WO2016199193A1 - Gasification device, substrate processing device and semiconductor device production method - Google Patents

Abstract

[Problem] To provide a technique for generating stably a gasified gas in a liquid gasification process. [Solution] The gasification device comprises: a gasification container having an introduction port and an discharge port for a carrier gas; a dripping nozzle constituted in such a manner as to drip into a gasification container a liquid containing two or more substances whereof the boiling points inside the gasification container are different; a first gasification surface, which is horizontal or is inclined with respect to the horizontal, provided inside the gasification container at a dripping position of the liquid from the dripping nozzle; a heater for heating the first gasification surface; and an inclination angle adjustment mechanism for adjusting the inclination angle of the first gasification surface.

Description

Evaporation apparatus, substrate processing apparatus, and semiconductor device manufacturing method

The present invention relates to a vaporizer, a substrate processing apparatus, and a method for manufacturing a semiconductor device.

With the miniaturization of a large scale integrated circuit (hereinafter referred to as LSI), a processing technique for controlling leakage current interference between transistor elements has increased technical difficulties. LSI element separation is performed by forming a gap such as a groove or a hole between elements to be separated in silicon (Si) serving as a substrate and depositing an insulator in the gap. As an insulator, a silicon oxide film (SiO ₂ ) is often used, and oxidation of the silicon substrate itself, chemical vapor deposition (hereinafter referred to as CVD), insulating coating method (Spin On Dielectric: hereinafter referred to as SOD). ).

Due to the recent miniaturization, the filling method by the CVD method is reaching the technical limit with respect to the filling of the fine structure, particularly the filling of the oxide into the void structure deep in the vertical direction or narrow in the horizontal direction. In view of such a background, the embedding method using an oxide having fluidity, that is, the adoption of SOD has been studied. In SOD, for example, a coating insulating material containing an inorganic or organic component called SOG (Spin On Glass) is used. This material has been used in LSI manufacturing processes before the advent of CVD oxide films. When the processing technique has a processing dimension of about 0.35 μm to 1 μm, the modification method after coating was allowed to perform heat treatment at about 400 ° C. in a nitrogen atmosphere. However, in recent LSIs, the minimum processing dimension typified by DRAM (Dynamic Random Access Memory) and Flash Memory is smaller than 50 nm width, and polysilazane is being considered as a material to replace SOG.

Polysilazane is, for example, a material obtained by a catalytic reaction of dichlorosilane or trichlorosilane and ammonia, and is applied onto a substrate using a spin coater when forming a thin film. The film thickness of the coating film is adjusted by the molecular weight, viscosity, and coater rotation speed of polysilazane.

Polysilazane contains nitrogen derived from ammonia as an impurity from the manufacturing process. Therefore, in order to remove impurities from the coating film formed using polysilazane and obtain a dense oxide film, it is necessary to add water and perform heat treatment after coating. As a method of adding moisture, a method of generating moisture by reacting hydrogen and oxygen in a heat treatment furnace is known. The generated moisture is taken into the polysilazane film, and heat is applied to obtain a dense oxide film. The heat treatment performed at this time is STI (Shallow Trench Isolation) for element isolation, and the maximum temperature may reach about 1000 ° C. in some cases.

While polysilazane is widely used in LSI processes, there is an increasing demand for reducing the thermal load of transistors. The reason for reducing the thermal load is to prevent excessive diffusion of impurities such as boron, arsenic, and phosphorus implanted for transistor operation, prevent aggregation of metal silicide for electrodes, and work function metal materials for gates. There are performance fluctuation prevention, memory element writing and reading, ensuring repeated life. Therefore, the ability to efficiently apply moisture in the process of applying moisture directly leads to a reduction in heat load in the heat treatment performed thereafter.

JP 2010-87475 A

An object of the present invention is to provide a technique capable of improving the manufacturing quality of a semiconductor device and improving the manufacturing throughput.

According to one aspect of the present invention, a reaction chamber that processes a substrate, a vaporizer that vaporizes a treatment liquid containing two or more substances having different boiling points, and generates a process gas, and the vaporizer generated in the vaporizer A vaporizing device having a processing gas introduction nozzle for introducing the processing gas into the reaction chamber and an exhaust system for exhausting the atmosphere in the reaction chamber; and the vaporizer having a carrier gas introduction port and a discharge port at both ends. A container, a dropping nozzle configured to drop the treatment liquid into the vaporization container in the vaporization container, a position where the treatment liquid is dropped from the dropping nozzle in the vaporization container, and the vaporization A first vaporization surface having a horizontal or horizontal inclination along a direction from one end to the other end of the container, a heater for heating the first vaporization surface, and an inclination of the first vaporization surface And inclination angle adjusting mechanism for changing the degree, technology with the are provided.

According to the present invention, there is provided a technique capable of improving the manufacturing quality of a semiconductor device and improving the manufacturing throughput.

It is a block diagram of the substrate processing apparatus which concerns on one Embodiment of this invention. (A) It is structural drawing of vaporization apparatus 114A which concerns on one Embodiment of this invention, Comprising: It is a figure which shows a 1st state. (B) It is structural drawing of the vaporization apparatus 114A which concerns on one Embodiment of this invention, Comprising: It is a figure which shows a 2nd state. It is a structural example of the controller which concerns on one Embodiment of this invention. (A) It is structural drawing of the vaporization apparatus 114B which concerns on one Embodiment of this invention, Comprising: It is a figure which shows a 1st state. (B) A structural diagram of the vaporizer 114B according to an embodiment of the present invention, showing a second state. It is a side view which shows the shape of the vaporization pipe | tube used for the modification 1 of the vaporization apparatus which concerns on one Embodiment of this invention. (A) It is a side view which shows the shape of the vaporization pipe | tube used for the modification 2 of the vaporization apparatus which concerns on one Embodiment of this invention. (B) It is a front view which shows the shape of the vaporization pipe | tube used for the modification 2 of the vaporization apparatus which concerns on one Embodiment of this invention. It is a side view which shows the shape of the vaporization pipe | tube used for the modification 3 of the vaporization apparatus which concerns on one Embodiment of this invention. (A) It is a side view which shows the shape of the vaporization pipe | tube used for the modification 4 of the vaporization apparatus which concerns on one Embodiment of this invention. (B) It is a perspective view which shows the shape of the vaporization pipe | tube used for the modification 4 of the vaporization apparatus which concerns on one Embodiment of this invention. It is a block diagram of the vaporization apparatus 114C which concerns on one Embodiment of this invention. It is an example of a flow of a substrate processing process concerning one embodiment of the present invention.

<First Embodiment of the Present Invention>
Hereinafter, an embodiment of the present invention will be described.

(1) Configuration of Substrate Processing Apparatus First, a configuration example of a substrate processing apparatus that implements the semiconductor device manufacturing method according to the present embodiment will be described with reference to FIG. The substrate processing apparatus is an apparatus that processes a substrate using a processing gas generated by vaporizing a liquid containing oxygen. For example, it is an apparatus for processing a wafer 100 as a substrate made of silicon or the like. This substrate processing apparatus is suitable for use in processing a substrate (wafer 100) having a concavo-convex structure (void) that is a fine structure. A substrate having a fine structure refers to a substrate having a structure with a high aspect ratio, such as a laterally narrow groove (concave portion) having a width of about 10 nm to 50 nm.

As illustrated in FIG. 1, the substrate processing apparatus includes a gas supply unit (gas supply system), a reaction chamber 104, a boat 102 that holds a plurality of wafers 100, and a reaction chamber heating unit that heats the wafers 100. The chamber heater 103, an exhaust unit (exhaust system) for exhausting the atmosphere in the reaction chamber, and the controller 200 are configured. The gas supplied from the gas supply unit is introduced into the reaction chamber 104 through the gas introduction nozzle 101a.

<Gas supply unit>
Next, the gas supply unit (gas supply system) will be described. The gas supply unit includes a gas introduction nozzle 101 a that supplies a processing gas into the reaction chamber 104. As needed, you may comprise so that at least 1 or more of the process liquid supply unit 101b, the vaporization unit 101c as a vaporization part, and the drain 101d may be included.

The processing liquid supply unit 101b includes a processing liquid tank 106a, a processing liquid spare tank 106b, a purge water supply section 107, a purge air supply section 108, a processing liquid pump 109, and manual valves 110a, 110b, 110c, 110d and automatic valves 111a, 111b, and 111c controlled by the controller 200.

The purge water supply unit 107, the purge air supply unit 108, and the manual valves 110a and 110b are used during maintenance of the processing liquid supply unit 101b, that is, when cleaning the inside of the processing liquid supply unit 101b, and the manual valves 110a and 110b. Is normally closed.

The treatment liquid tank 106a and the treatment liquid reserve tank 106b contain a liquid containing oxygen as a treatment liquid. The liquid containing oxygen is, for example, at least one of hydrogen peroxide (H ₂ O ₂ ), ozone (O ₃ ), nitrous oxide (NO), carbon dioxide (CO ₂ ), and carbon monoxide (CO). Or a liquid containing any two or more. In the following example, an example using a hydrogen peroxide solution, that is, an aqueous solution containing H ₂ O ₂ will be described.

The vaporization unit 101c includes a liquid flow rate control device 113, a vaporization device 114, a reserve tank 115, manual valves 110e, 110f, and 110g for partitioning them, automatic valves 111d to n that are controlled by the controller 200, and a mass flow controller (MFC). 118, 120.

Purge gas (inert gas) is supplied from the purge gas supply source 112 to the reserve tank 115 via the automatic valve 111d. The purge gas supply source 112 is also connected to the automatic valve 111m and the MFC 119. Here, the purge gas is an inert gas such as nitrogen (N ₂ ) gas.

The reserve tank 115 is used to adjust the supply pressure of the processing liquid to the liquid flow rate control device 113. The liquid supplied from the processing liquid pump 109 may not be a continuous flow. Accordingly, the processing liquid supplied from the processing liquid supply unit 101b is supplied to the reserve tank 115, and the processing liquid is pushed out to the liquid flow rate control device 113 by the pressure of the gas supplied from the purge gas supply source 112. . By using the gas pressure, the supply amount of the processing liquid can be made constant. The vaporizer 114 is continuously supplied with the treatment liquid whose flow rate is adjusted by the liquid flow controller 113, thereby vaporizing a constant amount of the treatment liquid and supplying the gas generated by the vaporization to the reaction chamber 104. It is like that.

The oxygen-containing gas supply source 117 is connected to the automatic valve 111m and the MFC 120, and supplies the oxygen-containing gas to the vaporizer 114. The oxygen-containing gas supply source 117 is connected to the automatic valve 111o and the MFC 118. The pipe connected to the downstream side of the MFC 118 merges with the pipe connected to the downstream side of the MFC 119 for adjusting the flow rate of the purge gas. Further, the joined pipe joins with the pipe connected to the downstream side of the vaporizer 114 via the automatic valve 111L. Here, the oxygen-containing gas is, for example, any of oxygen (O ₂ ), water (H ₂ O), O ₃ , nitrous oxide (NO), nitrogen dioxide (NO ₂ ), or a mixed gas thereof. . In the present embodiment, oxygen gas is particularly used as the oxygen-containing gas. In addition, a nitrogen-containing gas may be supplied in order to nitride the formed oxide film. The nitrogen-containing gas is, for example, N ₂ , ammonia (NH ₃ ), or a mixed gas thereof.

The above hydrogen peroxide solution may react with a metal. Therefore, the gas introduction nozzle 101a, the vaporization unit 101c, and the treatment liquid supply unit 101b are configured by a member having a protective film. For example, a member using aluminum uses alumite (Al ₂ O ₃ ), and a member using stainless steel uses a chromium oxide film. Further, ceramics such as Al ₂ O ₃ , AlN, and SiC other than metals, or quartz members may be used. Moreover, about the instrument which is not heated, you may comprise with the material which does not react with process liquids, such as Teflon (trademark) and a plastics.

The exhaust part is composed of an exhaust valve 105a. The exhaust pump 105b may be included as necessary.

<Configuration of vaporizer 114A>
Here, the detailed structure of the vaporization apparatus 114 which concerns on 1st Embodiment is demonstrated using the vaporization apparatus 114A of FIG. FIG. 2A is a structural diagram (sectional view) in one state of the vaporizer 114A. FIG. 2B is a structural diagram (sectional view) in another state of the same vaporizer 114A.

The vaporizer 114A uses a dropping method in which the treatment liquid is vaporized by dropping the treatment liquid into a heated vaporization container. The vaporizer 114 </ b> A includes a dripping nozzle 300 as a processing liquid supply unit, a vaporization tube 302 that constitutes a vaporization container to be heated, a vaporization space 301 that is constituted by the vaporization tube 302, and a heating unit that heats the vaporization tube 302 ( A vaporizing heater 303 as a heater), a carrier gas introduction port 307 for introducing a carrier gas into the vaporizing pipe from one end of the vaporizing pipe 302, and a gas generated by vaporizing the carrier gas and the processing liquid from the other end of the vaporizing pipe 302. A carrier gas discharge port 308 that discharges from the vaporization pipe, a thermocouple 305 that is a sensor for measuring the temperature of the vaporization pipe 302, and a temperature controller that controls the temperature of the vaporization heater 303 based on the temperature measured by the thermocouple 305. 400, the treatment liquid supply pipe 309 for supplying the treatment liquid to the dropping nozzle 300, and the inclination angle of the vaporization pipe 302 are changed. Inclination angle adjusting mechanism 310, and a city. A processing liquid is supplied from the liquid flow control device 113 to the processing liquid supply pipe 309. An oxygen gas, which is an oxygen-containing gas, is supplied from the MFC 120 to the carrier gas introduction port 307 as a carrier gas. The temperature of the vaporizing heater 303 is controlled by the temperature controller 400 controlling the output of the vaporizing heater power supply 304.

In the vaporizer 114A according to the present embodiment, it is necessary that the dropped treatment liquid is quickly vaporized on the surface of the vaporization tube 302, and therefore it is desirable to make the droplets dropped from the dropping nozzle 300 small. Specifically, for example, the size of a spherical droplet is 2 to 3 mm, and the flow rate is about 1.5 cc / min. Further, in order to reduce the size of the droplet, the dropping nozzle 300 uses, for example, a resin tube having a diameter of 1/16 inch. Further, since it is necessary to control the flow rate of the processing liquid supplied to the dropping nozzle 300 at a minute flow rate, the liquid flow rate control device 113 is used. A tube pump can also be used as the liquid flow rate control device.

The vaporizing tube 302 is heated by the vaporizing heater 303 so that the dripped processing liquid quickly vaporizes when contacting the vaporizing tube 302. Further, a heat insulating material 306 is provided in order to improve the heating efficiency of the vaporization container 302 by the vaporization heater 303 and to insulate the vaporization device 114A from other units. The vaporization tube 302 is made of quartz (particularly anhydrous transparent quartz or synthetic quartz), silicon carbide, or the like in order to prevent reaction with the treatment liquid. Further, the temperature of the vaporizing tube 302 is lowered by the temperature of the dropped processing liquid and the heat of vaporization. Therefore, it is effective to use silicon carbide having high thermal conductivity in order to prevent a temperature drop. In the present embodiment, the vaporization heater 303 is configured by a heating wire or the like. However, the present invention is not limited to this, and a lamp heater (radiation heater) can also be used. Examples of lamp heaters include Kanthal wire heaters, carbon heaters, SiC heaters, tungsten lamps, and halogen lamps.

Here, when a liquid in which two or more raw materials having different boiling points are heated and vaporized as the treatment liquid, even if the liquid is heated at a temperature higher than the boiling point of the treatment liquid, the entire liquid is not heated uniformly. As a result, only the vaporization of one specific raw material having a low boiling point contained in the treatment liquid proceeds first, and the vaporization of other raw materials may not proceed. As a result, the concentration of other raw materials may occur in the heated treatment liquid, and there may be unevenness in the concentration ratio of the finally vaporized gas.

More specifically, in this embodiment, the hydrogen peroxide solution is vaporized as a liquid in which raw materials having different boiling points are mixed. Since hydrogen peroxide water contains H ₂ O ₂ gas in H ₂ O, its boiling point varies depending on the concentration of dissolved hydrogen peroxide gas. For example, in the case of 34% hydrogen peroxide, the boiling point in atmospheric pressure is approximately 106 ° C. However, in the case of 100% concentration hydrogen peroxide, the boiling point is about 150 ° C., and the boiling point of water is 100 ° C. Therefore, for example, when trying to evaporate the hydrogen peroxide solution stored in the container by the boiling method, as described above, the hydrogen peroxide solution in the container is not uniformly heated, so that only water preferentially evaporates, Concentration of hydrogen peroxide occurs in the hydrogen peroxide solution as the treatment liquid.
Therefore, in the present embodiment, hydrogen peroxide is concentrated by rapidly heating the entire hydrogen peroxide solution on the heating surface at a temperature higher than the boiling point of the hydrogen peroxide solution having a boiling point higher than that of water. To prevent. More specifically, for example, when vaporizing and vaporizing 34% hydrogen peroxide solution at atmospheric pressure, the vaporizing tube 302 is heated to a temperature higher than 106 ° C., which is the boiling point of 34% hydrogen peroxide solution, By dropping the hydrogen peroxide solution on the heating surface of the vaporizing tube 302, the hydrogen peroxide solution droplets are heated quickly at 106 ° C. or more to vaporize the hydrogen peroxide solution. Further, in order to more reliably prevent the concentration of hydrogen peroxide, even when the vaporization tube 302 is heated to a temperature higher than 150 ° C., which is the boiling point of 100% concentration hydrogen peroxide, the hydrogen peroxide solution is vaporized. Good.

However, since hydrogen peroxide has the property that decomposition is accelerated as the heating temperature increases, it is necessary to heat the hydrogen peroxide solution at the lowest possible temperature while suppressing the concentration of hydrogen peroxide. There is. In particular, decomposition of hydrogen peroxide is rapidly accelerated when the temperature exceeds 150 ° C. Therefore, in the present embodiment, the vaporization heater is used to heat the hydrogen peroxide solution at a temperature as low as possible that is higher than the boiling point of the predetermined concentration hydrogen peroxide solution that is the treatment liquid and that does not cause concentration of hydrogen peroxide. The temperature of 303 is controlled.

The vaporization tube 302 in the present embodiment has, in particular, a first vaporization surface 302a that comes into contact with the treatment liquid dropped from the dropping nozzle 300. FIG. 2A shows a state in which the first vaporization surface 302a according to the present embodiment has an inclination (for example, 5 °) that decreases with respect to the horizontal. The first vaporization surface 302a is configured such that the inclination is adjusted by an inclination angle adjusting mechanism 310 described later.

In the present embodiment, the thermocouple 305 measures the temperature of the first vaporization surface 302a (or the vicinity of the first vaporization surface of the vaporization heater 303), in particular, near the point where the treatment liquid is dripped from the dropping nozzle 300. To be provided. Therefore, the temperature controller 400 controls the temperature of the vaporization heater 303 based on the temperature of the first vaporization surface 302a, particularly the temperature near the point where the treatment liquid is dropped, and heats the first vaporization surface 302a. .

When vaporizing the treatment liquid using the vaporization tube 302 configured as described above, the treatment liquid dropped from the dropping nozzle 300 first comes into contact with the first vaporization surface 302a. The treatment liquid that has come into contact with 302a is heated on the vaporization surface, and gradually flows through the vaporization surface by being pushed by the flow of the carrier gas introduced from the carrier gas introduction port 307. In addition, when the first vaporization surface 302a has an inclination in the downward direction, the processing liquid flows along the inclination direction. The vaporized gas generated by vaporizing the treatment liquid is discharged from the carrier gas discharge port 308 together with the carrier gas.

However, when the processing liquid is to be vaporized in the vaporizing tube 302, the following undesirable state may occur.
(I) In the process of vaporizing the treatment liquid on the first vaporization surface 302a, when the dropped treatment liquid flows slowly or does not flow on the vaporization surface, a droplet of the treatment liquid is applied to the same portion on the vaporization surface. The time for staying longer. As a result, the amount of heat per unit time taken away by the treatment liquid increases in that portion, so that a temperature drop locally occurs in the vaporization plane, and uneven temperature distribution occurs in the vaporization plane. When the heating temperature is lowered, as described above, only the vaporization of H ₂ O in the treatment liquid (hydrogen peroxide solution) easily proceeds, and concentration may occur in the droplets of the treatment liquid.

(Ii) Further, a droplet of the treatment liquid may remain in the same portion on the vaporization surface, resulting in a liquid pool. When the treatment liquid in the liquid pool state is heated, the entire treatment liquid is less likely to be heated evenly, so that the concentration of the treatment liquid is further facilitated. Further, when the treatment liquid in the liquid pool state is heated, the treatment liquid may not be completely vaporized and may be discharged from the vaporizer 114A together with the carrier gas in a state where vaporization is incomplete. Here, the state of incomplete vaporization means a state in which the treatment liquid is not completely in a gaseous state. For example, a cluster state in which some molecules of the treatment liquid are combined or a number of clusters are collected. It means that it is in a mist state.

As will be described later, in the present embodiment, when a vaporized gas of hydrogen peroxide, which is a treatment liquid, is introduced into a reaction chamber to oxidize a substrate having a film coated with polysilazane, vaporization of the treatment liquid is not required. When supplied into the reaction chamber in a complete state, there is a possibility that a processing liquid (a processing liquid in a cluster state or a mist state) in an incomplete vaporization state becomes particles. Therefore, it is desirable that the vaporized gas used in the present embodiment is in a complete gas state. Therefore, it is desirable to prevent liquid accumulation from occurring on the vaporized surface.
However, it is not always necessary to use only the vaporized gas in a complete gas state, depending on the case where it is used for other purposes other than the present embodiment, or depending on the required processing quality and the allowable range of the generation amount of particles, A gas containing a treatment liquid in a mist state may be used.

(Iii) Moreover, the thermocouple 305 used for temperature control of the vaporization heater 303 is configured to measure only the temperature of a specific point (or the vicinity thereof) in the first vaporization surface 302a. Therefore, when the temperature in the vicinity of the thermocouple 305 is locally decreased, control is performed to increase the output of the vaporization heater 303 in order to increase the temperature. As a result, the vaporization surface of the part other than the part where the temperature has locally decreased is overheated, and when the treatment liquid comes into contact with such an overheated part, hydrogen peroxide in the treatment liquid is reduced. There is a possibility of decomposing. In addition, when the temperature locally decreases in a portion other than the vicinity of the thermocouple 305, the temperature of the portion where the temperature has decreased is not compensated, and thus a local low temperature state is maintained.

(Iv) Depending on the flow speed of the treatment liquid and the vaporization speed, the treatment liquid may reach the carrier gas discharge port 308 without being vaporized on the first vaporization surface 302a. As a result, liquid leakage from the carrier gas discharge port 308 occurs, or liquid accumulation occurs in the vicinity thereof.

Here, in order to avoid a local temperature drop on the vaporization surface, it is conceivable to set the temperature of the vaporization heater 303 high in advance. However, as described above, since hydrogen peroxide has a property that decomposition is promoted as the heating temperature increases, it is not desirable to heat it excessively.

In the present embodiment, only one thermocouple is used, and the vaporization heater is configured to heat the entire first vaporization surface 302a with a single heater. However, a plurality of thermocouples and vaporization heaters are provided in the vaporization surface. It is also possible to provide each of the regions individually and control each region to be individually heated. By comprising in this way, the nonuniformity of the temperature distribution in a vaporization surface can be suppressed. However, by providing multiple thermocouples and vaporization heaters on the same vaporization surface, it is possible to suppress such uneven temperature distribution to a certain extent.However, the cost of the apparatus increases and temperature control by the temperature controller is difficult. is there.

Therefore, in this embodiment, the inclination of the vaporization surface can be adjusted by providing the inclination angle adjusting mechanism 310. Thereby, the unevenness of the temperature distribution in the vaporization plane can be easily suppressed without increasing the apparatus cost and making complicated temperature control unnecessary. Further, the flow rate of the processing liquid can be adjusted so that the processing liquid does not reach the carrier gas discharge port 308. Hereinafter, the configuration of the tilt angle adjusting mechanism 310 and the procedure for adjusting the tilt angle using the mechanism will be described.

As shown in FIGS. 2A and 2B, the vaporizer 114A is provided with an inclination angle adjustment mechanism 310 for changing the inclination angle of the vaporization tube 302 (more precisely, the first vaporization surface 302a). ing. The inclination angle adjusting mechanism 310 is a direction in which the carrier gas introduced from the carrier gas introduction port 307 flows in a direction that is lowered with respect to the horizontal (hereinafter, positive inclination direction) or a direction that is raised with respect to the horizontal ( Hereinafter, the inclination of the first vaporization surface 302a can be changed in the negative inclination direction). FIG. 2 (b) shows a state where the inclination of the vaporizing tube 302 is changed in the negative inclination direction with respect to the state of FIG. 2 (a). In the state of FIG. 2B, since the inclination angle is shallower than in the state of FIG. 2A, the flow rate of the processing liquid is slow.

Further, the vaporizer 114A is provided with a level attachment plate 311 for attaching a level when measuring the level of the vaporization tube 302. The level attachment plate 311 is provided so as to be parallel to the first vaporization surface 302a. By attaching a level to this plate, the level of the vaporization surface is easily measured and the inclination angle is adjusted. be able to.

[Tilt angle adjustment procedure]
The adjustment of the tilt angle by the tilt angle adjusting mechanism 310 is performed by the following procedure, for example. First, the treatment liquid is dropped from the dropping nozzle 300 onto the first vaporization surface 302a. At this time, the dropping speed, the temperature control parameter of the vaporizing heater 303 in the temperature controller 400, and the like are set in advance, and the vaporizing tube 302 is heated by the vaporizing heater 303. Here, since the dropped processing liquid flows slowly on the first vaporization surface 302a or does not flow, when the processing liquid is locally retained on the vaporization surface, the inclination angle is positively inclined. Adjust (change) in the direction. As a result, the flow rate of the treatment liquid increases, so that local retention of the treatment liquid is eliminated, and the temperature distribution on the vaporization surface can be made closer to uniform.

On the other hand, the dropped treatment liquid flows at a high speed on the first vaporization surface 302a, and the treatment liquid reaches the carrier gas discharge port 308 at the end of the vaporization pipe 302 before it is completely vaporized on the first vaporization surface 302a. If the state is reached, the tilt angle is adjusted (changed) in the negative tilt direction. This slows down the flow rate of the processing liquid, so that all the processing liquid can be vaporized before reaching the carrier gas discharge port 308.

In order to make the temperature distribution in the first vaporization surface 302a close to uniform, it is desirable that all of the dropped treatment liquid is vaporized immediately before the carrier gas discharge port 308. Therefore, in the adjustment procedure of the inclination angle of the vaporization surface, it is desirable to repeat the adjustment procedure so that the treatment liquid finally has an inclination angle that vaporizes immediately before the carrier gas discharge port 308. Further, when it is difficult to realize the above-described desirable state only by adjusting the inclination angle, the temperature of the vaporizing heater 303 may be adjusted.

Note that the dropped treatment liquid may move on the vaporization surface by being pushed by the flow of the carrier gas introduced from the carrier gas introduction port 307 in addition to the case where the vaporization surface is inclined. Therefore, the inclination of the vaporization surface does not always have to be inclined in the positive inclination direction, and may be adjusted so as to be inclined in the horizontal or negative inclination direction with respect to the horizontal.

For example, the following advantageous effects can be obtained by generating the vaporized gas of the processing liquid using the vaporizer 114A according to the present embodiment.
[Advantageous Effects of Vaporizer 114A]
(A) By adjusting the inclination angle of the first vaporization surface 302a using the inclination angle adjustment mechanism 310, the temperature distribution of the vaporization surface can be made uniform as described above, so the thermocouple 305 and the vaporization heater Even in the case where 303 is provided with only one each, it is possible to prevent the vaporized surface from being excessively heated or the vaporized surface from becoming a low temperature state. Further, even when the thermocouple and the vaporization heater are individually provided for a plurality of regions on the vaporization surface, the temperature distribution in the vaporization surface is almost uniform, so that the temperature control in each region can be easily performed.

(B) Particularly when hydrogen peroxide water is used as the treatment liquid, it is important to control the heating temperature to be within a predetermined temperature range because decomposition of hydrogen peroxide proceeds when heated excessively. In this embodiment, since it is possible to adjust the temperature distribution on the vaporization surface so that the temperature distribution is nearly uniform, concentration in the droplets of hydrogen peroxide water does not occur at any location on the vaporization surface. The temperature can be controlled to be equal to or higher than the temperature at which vaporization is sufficiently rapid, and lower than the temperature at which decomposition of hydrogen peroxide is practically acceptable. Therefore, the hydrogen peroxide solution can be stably vaporized at the optimum temperature.

(C) Furthermore, a liquid containing two or more substances having different boiling points such as hydrogen peroxide solution can be stably vaporized at an optimal temperature so as not to cause concentration in the droplets. The vaporized gas maintaining the liquid ratio can be supplied to the reaction chamber. Therefore, reproducibility for each processing batch can be improved in the processing of the substrate to be processed with the vaporized gas. As will be described later, the vaporized gas of hydrogen peroxide water in the present embodiment is suitable as a processing gas when oxidizing a substrate on which a polysilazane film is formed.

(D) Moreover, the inclination of the vaporization surface can be adjusted to suppress the retention of liquid droplets of the processing liquid on the vaporization surface or the occurrence of liquid accumulation. Therefore, since the processing liquid is not heated in a state where the processing liquid is retained or in a liquid pool state, it is possible to prevent the processing liquid from being discharged together with the carrier gas in a state where vaporization is incomplete.

(E) The vaporizer may be installed in various places, and the place where it is installed is not always horizontal. Therefore, even if the control parameters of the temperature controller 400 and the dropping speed of the processing liquid are set to the optimum values in advance on the assumption that the installation location is horizontal, when it is installed at the actual installation location, Vaporization may not occur. As in the present embodiment, since the vaporizer includes an inclination angle adjustment mechanism, the inclination angle of the vaporization surface can be adjusted in accordance with the inclination of the actual installation location, so that the setting of control parameters and the like is greatly changed. And can be installed quickly.

(F) Since the flow rate of the treatment liquid on the vaporization surface is controlled by adjusting the inclination angle of the vaporization surface, the carrier gas flow (flow velocity) even when the treatment liquid moves in the vaporization tube due to the flow of the carrier gas. Or the flow rate), the flow rate of the processing liquid can be optimized.

<Control unit>
The controller 200 includes the above-described automatic valves 111a to 111n, the heater 103, the liquid flow rate control device 113, the gas supply unit, the exhaust unit, the temperature controller 400, and the vaporizer to perform the substrate processing steps described later. Control. As shown in FIG. 3, the controller 200, which is a control unit (control means), is configured as a computer including a CPU (Central Processing Unit) 200a, a RAM (Random Access Memory) 200b, a storage device 200c, and an I / O port 200d. Has been. The RAM 200b, the storage device 200c, and the I / O port 200d are configured to exchange data with the CPU 200a via the internal bus 200e. For example, an input / output device 201 configured as a touch panel or the like is connected to the controller 200.

The storage device 200c includes, for example, a flash memory, a HDD (Hard Disk Drive), and the like. In the storage device 200c, a control program that controls the operation of the substrate processing apparatus, a process recipe that describes the procedure and conditions of the substrate processing described later, and the like are stored in a readable manner. Note that the process recipe is a combination of functions so that a predetermined result can be obtained by causing the controller 200 to execute each procedure in a substrate processing step to be described later, and functions as a program. Hereinafter, the process recipe, the control program, and the like are collectively referred to as simply a program. When the term “program” is used in this specification, it may include only a process recipe alone, may include only a control program alone, or may include both. The RAM 200b is configured as a memory area (work area) in which programs, data, and the like read by the CPU 200a are temporarily stored.

The I / O port 200d includes the heater 103, the exhaust valve 105a, the exhaust pump 105b, the purge water supply unit 107, the purge air supply unit 108, the processing liquid pump 109, the automatic valves 111a to 111n, the MFCs 118 to 120, and the liquid flow rate control device. 113, connected to the temperature controllers 306 and 400. The temperature controller 400 is connected to control the vaporization heater power supply 303 and acquire a temperature signal from the thermocouple 305.

The CPU 200a is configured to read and execute a control program from the storage device 200c, and to read a process recipe from the storage device 200c in response to an operation command input from the input / output device 201 or the like. Then, the CPU 200a adjusts the flow rate of the processing liquid by the liquid flow rate control device 113, the flow rate adjustment operation of the purge water by the purge water supply unit 107, and the flow rate of the purge gas by the purge air supply unit 108 in accordance with the contents of the read process recipe. The adjusting operation, the opening / closing operation of the automatic valves 111a to 111n, the opening adjusting operation of the exhaust valve 105a, the temperature control operation by the temperature controllers 306 and 400, and the like are controlled.

The controller 200 is an external storage device (for example, a magnetic tape, a magnetic disk such as a flexible disk or a hard disk, an optical disk such as a CD or a DVD, a magneto-optical disk such as an MO, a USB memory (USB Flash Drive), a memory card, or the like. The above-mentioned program stored in the (semiconductor memory) 123 can be configured by installing it in a computer. The storage device 200c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these are collectively referred to simply as a recording medium. When the term “recording medium” is used in this specification, it may include only the storage device 200c alone, may include only the external storage device 123 alone, or may include both. The program may be provided to the computer using communication means such as the Internet or a dedicated line without using the external storage device 123.

<Configuration of vaporizer 114B>
Subsequently, as another example of the vaporizer according to the present embodiment, the configuration of the vaporizer 114B will be described. 4 (a) and 4 (b) are diagrams showing the configuration of the vaporizer 114B, the state before and after the inclination angle of the vaporization tube 302 of the same vaporizer 114B is adjusted by the inclination angle adjustment mechanism 310. FIG. Is shown. The same components as those of the vaporizer 114A are denoted by the same reference numerals.

The vaporizer 114B is different from the vaporizer 114A in the following points. In other respects, the vaporizer 114B has the same configuration as the vaporizer 114A.

4 (a), the vaporizer 114B further includes a second vaporization surface 302b on the downstream side of the first vaporization surface 302a. Here, the downstream side refers to the direction toward the carrier gas discharge port 308 as viewed from the carrier gas introduction port 307 (the direction in which the carrier gas introduced from the carrier gas introduction port 307 flows). In the state shown in FIG. 4A, the first vaporization surface 302a has an inclination that is lowered with respect to the horizontal (inclined in the positive inclination direction). On the other hand, unlike the first vaporization surface 302a, the second vaporization surface 302b has an inclination that is lower than the horizontal or the inclination angle of the first vaporization surface 302a. ing. (Especially in the state shown in FIG. 4A, it is in a horizontal state.)

Here, the inclination angle adjusting mechanism 310 included in the vaporizer 114B has a mechanism that changes the inclination angles of the first vaporization surface 302a and the second vaporization surface 302b in the same direction. Therefore, when the inclination of the first vaporization surface 302a is changed in the negative inclination direction, the inclination of the second vaporization surface 302b is similarly changed in the negative inclination direction.

Also, the vaporizer 114B is provided with a level attachment plate 311 for attaching a level when measuring the level of the vaporizer tube 302, as with the vaporizer 114A. The level attachment plate 311 is provided so as to be parallel to the first vaporization surface 302a. By attaching a level to this plate, the level of the vaporization surface is easily measured and the inclination angle is adjusted. be able to. The level attachment plate 311 may be provided so as to be parallel to the second vaporization surface 302b so that the inclination angle of the second vaporization surface 302b can be measured.

FIG. 4B shows a state in which the inclination of the vaporization tube 302 (that is, the first vaporization surface 302a and the second vaporization surface 302b) is changed in the negative inclination direction by using the inclination angle adjusting mechanism 310. Show. Here, the inclination of the first vaporization surface 302a is adjusted from the positive inclination state to the horizontal state, and the inclination of the second vaporization surface 302b is adjusted from the horizontal state to the negative inclination state.

The vaporizer 114B is configured such that the inclination angles of the first vaporization surface 302a and the second vaporization surface 302b are different from each other. In addition, the inclination angle of the first vaporization surface 302a is configured to be smaller than the inclination angle of the second vaporization surface 302b in the negative inclination direction. (The inclination angle of the first vaporization surface 302a is configured to be larger than the inclination angle of the second vaporization surface 302b in the positive inclination direction.) That is, the flow rate of the dropped treatment liquid flows. Is smaller on the second vaporization surface 302b than on the first vaporization surface 302a.

For example, in the case of the state of FIG. 4A, the treatment liquid dropped from the dropping nozzle 300 is heated on the first vaporization surface 302a and gradually vaporized while being pushed by the flow of the carrier gas, so that the second It flows to the vaporization surface 302b. Since the inclination angle of the second vaporization surface 302b is smaller in the positive inclination direction than the first vaporization surface 302a, the flow rate of the processing liquid is relatively slow. Therefore, compared with the case where the first vaporization surface 302b is not provided, the possibility that the processing liquid reaches the carrier gas discharge port 308 is reduced. Further, in the state of FIG. 4B, the inclination angle of the second vaporization surface 302b is larger in the negative inclination direction than in the case of FIG. Therefore, it is possible to more reliably prevent the processing liquid from reaching the carrier gas discharge port 308.

The inclination angle adjustment procedure by the inclination angle adjustment mechanism 310 is substantially the same as that of the vaporizer 114A. That is, since the dropped processing liquid flows slowly on the first vaporization surface 302a or does not flow, when the processing liquid is locally retained on the vaporization surface, the first vaporization surface 302a Adjust (change) the tilt angle in the positive tilt direction. Further, in the vaporizer 114B, there is a possibility that a liquid pool is generated at the boundary portion between the first vaporization surface 302a and the second vaporization surface 302b. Therefore, the inclination angle of the second vaporization surface 302b may be adjusted in the positive inclination direction so that no liquid pool occurs at the boundary portion.

Similarly, when the dropped treatment liquid flows at a high speed on the second vaporization surface 302b and the treatment liquid reaches the carrier gas discharge port 308 before it is completely vaporized, the inclination angle is changed to a negative inclination direction. Adjust (change). In addition, since the speed at which the processing liquid flows on the first vaporization surface 302a is too high, the processing liquid may flow into the second vaporization surface 302b while being hardly vaporized on the first vaporization surface 302a. . In that case, the processing liquid stays on the second vaporization surface 302b or a liquid pool is generated. Therefore, the inclination angle of the first vaporization surface 302a is negatively set so as to extend the time for the treatment liquid to vaporize on the first vaporization surface 302a and reduce the amount of the treatment liquid flowing on the second vaporization surface 302b. Adjust (change) in the direction of the inclination.

Similarly to the vaporizer 114A, in order to make the temperature distribution in the first vaporization surface 302a and the second vaporization surface 302b close to uniform, all of the dropped treatment liquid is vaporized immediately before the carrier gas discharge port 308. desirable. Therefore, in the adjustment procedure of the inclination angle of the vaporization surface, it is desirable to repeat the adjustment procedure so that the treatment liquid finally has an inclination angle that vaporizes immediately before the carrier gas discharge port 308.

Similarly to the vaporizer 114A, the vaporizer 114B is configured to heat both the first vaporization surface 302a and the second vaporization surface 302b with only one thermocouple and the vaporization heater with a single heater. Yes. However, since the first vaporization surface 302a and the second vaporization surface 302b in the vaporizer 114B have different inclination angles, the temperature distributions of the two are more likely to be different than in the vaporizer 114B. For this reason, by providing a thermocouple and a vaporization heater individually on each vaporization surface, the vaporization surfaces may be individually heated to control the temperature distribution of the two to be close to each other. However, the increase in the cost of the apparatus and the difficulty of temperature control by the controller are the same as in the vaporizer 114A.

In the present embodiment using the vaporizer 114B, for example, the following advantageous effects can be further obtained as compared with the case where the vaporizer 114A is used.
[Advantageous Effects of Vaporizer 114B]
(G) Since the inclination angle of the second vaporization surface 302b is smaller in the positive inclination direction than the first vaporization surface 302a, the flow rate of the processing liquid is relatively slow. Therefore, it is possible to more reliably prevent the processing liquid from reaching the carrier gas discharge port 308 as compared with the case where the first vaporization surface 302b is not provided.

In the vaporizer 114B, the second vaporization surface 302b is directly connected to the first vaporization surface 302a and continuously arranged. However, the arrangement is not limited to this, and the first vaporization surface 302a and the first vaporization surface 302b are arranged. Another vaporization surface (for example, third and fourth vaporization surfaces) may be provided between the two vaporization surfaces 302b.

Moreover, the vaporizer 114B is configured to adjust the inclination angles of both the first vaporization surface 302a and the second vaporization surface 302b by the same angle by the inclination angle adjustment mechanism 310. Here, a tilt angle adjusting mechanism may be further provided so as to individually adjust the tilt angle of the first vaporization surface 302a and the tilt angle of the second vaporization surface 302b.

<Configuration of Modification 1 of Vaporizer 114A or B>
Subsequently, as another example of the vaporizer according to the present embodiment, the configuration of Modification 1 of the vaporizer 114A or 114B described above will be described. FIG. 5 is a side view showing the shape of the vaporizing tube 502 used in the vaporizing apparatus of the first modification.

The vaporizing tube 502 used in the vaporizing device according to the first modification corresponds to the vaporizing tube 302 in the vaporizing device 114A. The carrier gas introduction port 507 and the carrier gas discharge port 508 correspond to the carrier gas introduction port 307 and the carrier gas discharge port 308 in the vaporizer 114A, respectively.

The treatment liquid introduction port 500 is an introduction port for supplying a treatment liquid into the vaporization tube 302 as a treatment liquid supply unit, similarly to the dropping nozzle 300 in the vaporizer 114A. Although the treatment liquid introduction port 500 does not have a nozzle shape, it is desirable to supply the treatment liquid so as to be dropped from the treatment liquid introduction port 500 to the vaporization tube 302 as in the case of the vaporizer 114A.

Similarly to the vaporizer 114A, the vaporizer of Modification 1 includes a vaporizer as a heating unit (heater) that heats the vaporizer tube 502, a thermocouple that is a sensor that measures the temperature of the vaporizer tube 502, Based on the temperature measured by the thermocouple, a temperature controller that controls the temperature of the vaporization heater, a treatment liquid supply pipe that supplies the treatment liquid to the treatment liquid introduction port 500, and an inclination that changes the inclination angle of the vaporization pipe 502 An angle adjustment mechanism and a level mounting plate for mounting a level when measuring the level of the vaporizing tube 502 are provided.

Here, the inclination angle adjustment mechanism provided in the vaporizer of the first modification is such that the side (port side) provided with the carrier gas introduction port 507 and the carrier gas discharge port 508 is raised with respect to the direction of gravity, and the opposite side ( The inclination angle of the vaporizing tube 502 can be changed in a direction in which the tip side is lowered with respect to the direction of gravity (a positive inclination direction shown in FIG. 5). Similarly, the tilt angle adjusting mechanism lowers the side on which the carrier gas introduction port 507 and the carrier gas discharge port 508 are provided with respect to the direction of gravity and raises the opposite side with respect to the direction of gravity (FIG. 5). The inclination angle can be changed in the negative inclination direction shown in FIG.

In the vaporizer of Modification 1, the treatment liquid supplied from the treatment liquid introduction port 500 into the vaporization pipe 502 is supplied from the first straight portion 502a formed on the carrier gas introduction port side of the vaporization pipe 502, Vaporization occurs while flowing through the meandering portion 502b formed to meander in the horizontal direction to the second straight portion 502c formed on the carrier gas discharge port side. Here, the example of the vaporizing tube 502 is particularly effective for reliably vaporizing the treatment liquid in the meandering portion 502b. That is, by providing the meandering portion 502 b and increasing the length of the vaporizing tube 502, the treatment liquid can be completely vaporized while flowing to the carrier gas discharge port 508.

Further, the inclination of the vaporizing tube 502 is changed by using the inclination angle adjusting mechanism to adjust the inclination of the vaporization surface of the first straight portion 502a, the meandering portion 502b, and the second straight portion 502c, thereby treating the processing liquid. Can be completely vaporized while flowing to the carrier gas discharge port 508. For example, when the vaporization surface of the first straight part 502a is adjusted so as to incline in the positive inclination direction, part of the vaporization surface in the meandering part 502b is inclined in the negative inclination direction. Therefore, even if the first linear portion 502a is inclined in the positive inclination direction, the flow rate of the processing liquid on the vaporization surface is increased and the vaporization of the processing liquid does not progress, the negative portion in the meandering portion 502b. The treatment liquid can be reliably vaporized on the vaporization surface having the inclination direction.

<Configuration of Modification 2 of Vaporizer 114A or B>
Subsequently, as another example of the vaporizer according to the present embodiment, a configuration of Modification 2 of the vaporizer 114A or 114B described above will be described. FIG. 6A is a side view showing the shape of the vaporizing tube 602 used in the vaporizing apparatus of the second modification. FIG. 6B is a front view showing the shape of the vaporization pipe 602 viewed from the direction of a carrier gas introduction port 607 and a carrier gas discharge port 608 described later.

The vaporizing tube 602 in the vaporizing device of Modification 2 has a configuration corresponding to the vaporizing tube 302 in the vaporizing device 114A. The carrier gas introduction port 607 and the carrier gas discharge port 608 correspond to the carrier gas introduction port 307 and the carrier gas discharge port 308 in the vaporizer 114A, respectively. The treatment liquid introduction port 600 is an introduction port for supplying a treatment liquid into the vaporization tube 302 as a treatment liquid supply unit, like the dropping nozzle 300 in the vaporizer 114A.

Similarly to the vaporizer 114A, the vaporizer of Modification 2 includes a vaporizer as a heating unit (heater) that heats the vaporizer tube 602, a thermocouple that is a sensor that measures the temperature of the vaporizer tube 602, Based on the temperature measured by the thermocouple, a temperature controller that controls the temperature of the vaporization heater, a treatment liquid supply pipe that supplies the treatment liquid to the treatment liquid introduction port 600, and an inclination that changes the inclination angle of the vaporization pipe 602 An angle adjustment mechanism and a level attachment plate for attaching a level when measuring the level of the vaporizing tube 602 are provided.

Here, as shown in FIG. 6 (a), the tilt angle adjusting mechanism provided in the vaporizer according to the second modified example is arranged such that the side (port side) provided with the carrier gas introduction port 607 and the carrier gas discharge port 608 is in the direction of gravity. It is possible to change the inclination angle of the vaporizing tube 602 in the direction in which the opposite side (front end side) is lowered with respect to the direction of gravity (the positive inclination direction shown in FIG. 6A). Similarly, in the tilt angle adjusting mechanism, the side where the carrier gas introduction port 607 and the carrier gas discharge port 608 are provided is lowered with respect to the direction of gravity and the opposite side is raised with respect to the direction of gravity (FIG. 6). The inclination angle can be changed in the negative inclination direction shown in (a).

The vaporization pipe 602 includes a first straight line portion 602a formed on the carrier gas introduction port side, a second straight line portion 602c formed on the carrier gas discharge port side, a first straight line portion 602a, and a second straight line. It is a direction perpendicular to the horizontal direction with respect to the portion 602c, and is constituted by a third straight portion 602b provided so as to be inclined in the direction of gravity from the first straight portion 602a toward the second straight portion 602c. Is done. In the vaporizer of Modification 2, the treatment liquid supplied from the treatment liquid introduction port 600 into the vaporization tube 602 passes through the first straight part 602a, the third straight part 602b, and the second straight part 602c. Vaporized while flowing into. Here, in the example of the vaporizing tube 602, similarly to the example of the vaporizing tube 502, the third straight portion 602 b is provided to increase the length of the vaporizing tube 602, so that the processing liquid flows to the carrier gas discharge port 608. The treatment liquid can be completely vaporized.

<Configuration of Modification 3 of Vaporizer 114A or B>
Subsequently, as another example of the vaporizer according to the present embodiment, a configuration of Modification 3 of the vaporizer 114A or 114B described above will be described. FIG. 7 is a side view showing the shape of the vaporizing tube 702 used in the vaporizing device of Modification 3.

The vaporizing tube 702 used in the vaporizing device of Modification 3 has a configuration corresponding to the vaporizing tube 302 in the vaporizing device 114A. The carrier gas introduction port 707 and the carrier gas discharge port 708 are structures corresponding to the carrier gas introduction port 307 and the carrier gas discharge port 308 in the vaporizer 114A, respectively. The treatment liquid introduction port 700 is an introduction port for supplying a treatment liquid into the vaporization tube 302 as a treatment liquid supply unit, similarly to the dropping nozzle 300 in the vaporizer 114A.

Similarly to the vaporizer 114A, the vaporizer of Modification 3 includes a vaporizer as a heating unit (heater) that heats the vaporizer tube 702, a thermocouple that is a sensor that measures the temperature of the vaporizer tube 702, Based on the temperature measured by the thermocouple, a temperature controller that controls the temperature of the vaporization heater, a treatment liquid supply pipe that supplies the treatment liquid to the treatment liquid introduction port 700, and an inclination that changes the inclination angle of the vaporization pipe 702 An angle adjustment mechanism and a level attachment plate for attaching a level when measuring the level of the vaporization tube 702 are provided.

Here, the inclination angle adjusting mechanism provided in the vaporizer of Modification 3 is such that the side (port side) provided with the carrier gas introduction port 707 and the carrier gas discharge port 708 is raised with respect to the direction of gravity and the opposite side ( The inclination angle of the vaporizing tube 702 can be changed in a direction in which the tip side is lowered with respect to the direction of gravity (positive inclination direction shown in FIG. 7). Similarly, in the tilt angle adjusting mechanism, the side where the carrier gas introduction port 707 and the carrier gas discharge port 708 are provided is lowered with respect to the direction of gravity and the opposite side is raised with respect to the direction of gravity (FIG. 7). The inclination angle can be changed in the negative inclination direction shown in FIG.

In the vaporizer of Modification 3, the treatment liquid supplied from the treatment liquid introduction port 700 into the vaporization pipe 702 is supplied from the first straight portion 702a formed on the carrier gas introduction port side of the vaporization pipe 702, Vaporization occurs while flowing through the spiral portion 702b formed in a spiral shape in the direction of gravity and into the second straight portion 702c formed on the carrier gas discharge port side. Here, in the example of the vaporizing tube 702, like the vaporizing tube 502 of the first modification, the spiral portion 702 b is provided to increase the length of the vaporizing tube 702, so that the processing liquid flows to the carrier gas discharge port 708. The treatment liquid can be completely vaporized.

<Configuration of Modification 4 of Vaporizer 114A or B>
Then, the structure of the modification 4 of the above-mentioned vaporization apparatus 114A or 114B is demonstrated as another example of the vaporization apparatus which concerns on this embodiment. FIG. 8A is a side view showing the shape of the vaporization tube 802 used in the vaporization apparatus of the fourth modification. FIG. 8B is a perspective view showing the shape of the vaporizing tube 802.

The vaporizing tube 802 used in the vaporizing device according to the modified example 4 has a configuration corresponding to the vaporizing tube 302 in the vaporizing device 114A. The carrier gas introduction port 807 and the carrier gas discharge port 808 correspond to the carrier gas introduction port 307 and the carrier gas discharge port 308 in the vaporizer 114A, respectively. The treatment liquid introduction port 800 is an introduction port for supplying a treatment liquid into the vaporization tube 302 as a treatment liquid supply unit, similarly to the dropping nozzle 300 in the vaporizer 114A.

Further, the vaporizer of Modification 4 is similar to the vaporizer 114A, a vaporization heater as a heating unit (heater) for heating the vaporization tube 802, a thermocouple that is a sensor for measuring the temperature of the vaporization tube 802, and Based on the temperature measured by the thermocouple, a temperature controller that controls the temperature of the vaporization heater, a treatment liquid supply pipe that supplies the treatment liquid to the treatment liquid introduction port 800, and an inclination that changes the inclination angle of the vaporization pipe 802 An angle adjustment mechanism and a level attachment plate for attaching a level when measuring the level of the vaporization tube 802 are provided.

Here, the inclination angle adjusting mechanism provided in the vaporizer of the modification 4 raises the side (port side) on which the carrier gas introduction port 807 and the carrier gas discharge port 808 are provided with respect to the direction of gravity, and the opposite side ( The inclination angle of the vaporizing tube 802 can be changed in a direction (a positive inclination direction shown in FIG. 8) in which the distal end side is lowered with respect to the direction of gravity. Similarly, the tilt angle adjusting mechanism lowers the side on which the carrier gas introduction port 807 and the carrier gas discharge port 808 are provided with respect to the direction of gravity and raises the opposite side with respect to the direction of gravity (FIG. 8). The inclination angle can be changed in the negative inclination direction shown in FIG.

The vaporizing tube 802 is wound around the first straight portion 802a formed on the carrier gas introduction port side, the second straight portion 802c formed on the carrier gas discharge port side, and the second straight portion 802c. The spiral portion 802b is formed in a spiral shape in the horizontal direction. In the vaporizer of Modification 4, the treatment liquid supplied from the treatment liquid introduction port 800 into the vaporization tube 802 flows from the first straight portion 802a to the second straight portion 802c via the spiral portion 802b. Vaporized in between. Here, the example of the vaporizing tube 802 is similar to the example of the vaporizing tube 802, by providing the spiral portion 802 b to increase the length of the vaporizing tube 802, so that the processing liquid flows while flowing to the carrier gas discharge port 808. Can be completely vaporized. Note that in the case of the vaporizer of Modification 4 using the vaporization tube 802, the flow rate of the carrier gas introduced from the carrier gas introduction port 807 is adjusted so that the processing liquid is moved from upstream to downstream in the spiral portion 802b. It is desirable.

<Configuration of vaporizer 114C>
FIG. 9 is a diagram showing a configuration of the vaporizer 114C. As shown in FIG. 9, the vaporizer 114C is a vaporizer comprising a plurality of vaporizers 114A, more specifically vaporizers 114A-1 to A-8.

The carrier gas introduction ports 307 included in the vaporizers 114A-1 to A-8 are all connected to the MFC 120, and are configured to introduce carrier gas into each of them. Similarly, the carrier gas discharge ports 308 included in the vaporizers 114A-1 to A-8 are all connected by piping so as to join together, and the discharged carrier gas and the vaporized gas of the processing liquid pass through the gas introduction nozzle 101a. Via the reaction chamber 104. The dropping nozzles 300 included in the vaporizers 114A-1 to A-8 are all configured to be supplied with the processing liquid from the liquid flow rate controller 113. In order to individually control the dropping amount, the liquid flow rate control device 113 may be individually provided in each of the vaporization devices 114A-1 to A-8.

The vaporizers 114A-1 to A-8 are each provided with an inclination angle adjusting mechanism 310. Therefore, each vaporizer is configured to be able to adjust the inclination angle individually.

When a plurality of vaporizers are connected in parallel, each vaporizer has a considerable difference in vaporization characteristics. As in this embodiment, since the vaporizer includes the inclination angle adjustment mechanism, the inclination angle of each vaporizer can be adjusted individually and easily, so that the plurality of vaporizers have equivalent vaporization characteristics. Easy to adjust.

Thus, by providing the vaporizers 114A-1 to A-8 in parallel, the amount of vaporized gas generated can be increased.

Although FIG. 9 shows a configuration including a plurality of vaporizers 114A, a configuration including a plurality of other vaporizers according to the present invention, for example, the vaporizer 114B, and variations 1 to 4 of the vaporizer 114A or B may be used. . Moreover, it is good also as a structure which combines different vaporization apparatuses. (For example, the vaporizers 114A and 114B are combined.)

(2) Substrate Processing Step Next, with reference to FIG. 10, a substrate processing step that is performed as one step in the manufacturing process of the semiconductor device according to the present embodiment will be described. Such a process is performed by the above-described substrate processing apparatus. In the following description, the operation of each unit constituting the substrate processing apparatus is controlled by the controller 200.

Here, an example of forming a silicon oxide film that insulates each element constituting the semiconductor device will be described.

(Substrate loading step S10)
First, the wafer 100 coated with a film containing silicon element, nitrogen element, and hydrogen element is loaded on the boat 102, and the boat 102 is loaded into the reaction chamber 104. After the carry-in, the inside of the reaction chamber 104 is exhausted by the exhaust part (the exhaust valve 105a and the exhaust pump 105b), and the inert gas supplied from the purge gas supply source 112 is used to replace the gas in the reaction chamber 104. Density reduction is performed. Examples of the film containing silicon element, nitrogen element, and hydrogen element include a film having a silazane bond such as polysilazane and a plasma polymerization film of tetrasilylamine and ammonia.

(Substrate heating step S20)
The wafer 100 loaded into the reaction chamber 104 is heated to a desired temperature by a preheated heater 103. The desired temperature is, for example, room temperature (RT) to 200 ° C. when hydrogen peroxide is used as the treatment liquid. The temperature is preferably 40 to 100 ° C., for example, heated to 100 ° C.

(Vaporization step S30)
After the wafer 100 is loaded into the reaction chamber 104, the processing liquid is supplied from the processing liquid supply unit 101b to the vaporization unit 101c, and the vaporization unit 101c performs a vaporization process of hydrogen peroxide solution as the processing liquid. In the vaporization step, the treatment liquid pump 109 sends hydrogen peroxide solution from the treatment liquid tank 106a or the treatment liquid reserve tank 106b to the reserve tank 115. The reserve tank 115 is in a state where the surface of the hydrogen peroxide solution accumulated in the reserve tank 115 is pressurized by supplying an inert gas from the purge gas supply source 112. The hydrogen peroxide solution is supplied to the liquid flow rate control device 113 from the liquid delivery unit 116 provided below the liquid level by the pressure. The liquid flow rate control device 113 adjusts the flow rate of the hydrogen peroxide solution sent from the reserve tank 115 and sends it to the vaporizer 114. An oxygen-containing gas is supplied from the oxygen-containing gas supply source 117 to the vaporizer 114 via the automatic valve 111n and the MFC 120. The oxygen-containing gas is introduced into the vaporizer 114 as a carrier gas and supplied to the reaction chamber 104 together with the vaporized gas of the generated hydrogen peroxide solution. Here, in this embodiment, O ₂ gas is used as the oxygen-containing gas that is the carrier gas.

In the vaporizer 114, for example, as illustrated in FIG. 2, the hydrogen peroxide solution is dropped from the treatment liquid lower nozzle 300 to the vaporization tube 302 that is a heated vaporization container via the treatment liquid supply pipe 309. It has become. When the dropped hydrogen peroxide solution reaches the heated vaporizing tube 302, it is heated and evaporated to become a vaporized gas. The hydrogen peroxide that has become the vaporized gas flows from the carrier gas exhaust port 308 to the reaction chamber 104 together with the carrier gas introduced from the carrier gas introduction port 307. The hydrogen peroxide solution vaporization step may be performed before the wafer 100 loading step.

(Oxidation step S40)
After the wafer 100 is heated to a desired temperature, the automatic valve 111k is opened and a gas containing hydrogen peroxide vaporized is supplied from the vaporization unit 101c to the reaction chamber 104 to fill the reaction chamber 104. The film of polysilazane or the like applied on the wafer 100 is hydrolyzed by the supplied hydrogen peroxide. In addition, silicon generated by hydrolysis is oxidized by hydrogen peroxide to form a silicon oxide film. Note that the pressure in the reaction chamber 104 in the oxidation step may be a reduced pressure state or a pressure increased to atmospheric pressure or higher. A pressure of 50 kPa to 300 kPa (0.5 atm to 3 atm) is preferable. By pressurizing, the contact probability between the vaporized hydrogen peroxide and the wafer 100 can be increased, and the processing uniformity and processing speed can be improved. In order to make it equal to or higher than the atmospheric pressure, an exhaust stop process S50 for stopping exhaust by closing the exhaust valve 105a is performed.

In addition, by using hydrogen peroxide, one of the active species, hydroxy radical (OH *), can be generated in the reaction chamber 104. This active species makes it possible to oxidize polysilazane. OH * is a neutral radical in which oxygen and hydrogen are bonded, and has a simple structure in which hydrogen is bonded to an oxygen molecule.

Further, the inventors' diligent research has revealed that hydrogen peroxide has higher permeability than H ₂ O in a gaseous state. By using this property, the inside of the polysilazane coating film having a large film thickness or the inside of the polysilazane coating film formed in a minute space can be oxidized. Therefore, film characteristics such as dielectric constant characteristics in the depth (thickness) direction of the formed silicon oxide film and density characteristics of the film can be made uniform.

Further, by using hydrogen peroxide water as the treatment liquid, the polysilazane film formed on the substrate can be oxidized at a low temperature in a short time.

(Annealing step S60)
After the oxidation process of the polysilazane coating film using hydrogen peroxide, an annealing process is performed as necessary in order to improve the quality of the silicon oxide film formed on the wafer 100. After the automatic valve 111k is closed and the supply of the gas containing hydrogen peroxide supplied from the vaporizer 114 is stopped, the inert gas is supplied into the reaction chamber 104 by the purge gas supply source 112, and the reaction chamber 104 is The temperature is raised to a desired temperature in the range of 400 ° C. to 1100 ° C., and the temperature is maintained. Thereafter, an oxygen-containing gas is supplied from an oxygen-containing gas supply source 117 as necessary, and the silicon oxide film is annealed. In this embodiment, an oxygen gas is used as the oxygen-containing gas used for the annealing treatment, similar to the hydrogen peroxide carrier gas. However, the oxygen-containing gas used for the annealing treatment and the oxygen-containing gas used as the hydrogen peroxide carrier gas may be different. Further, a nitrogen-containing gas may be supplied in order to nitride the formed oxide film.

(Cooling step S70)
After the annealing step, the heated wafer 100 is cooled to a temperature at which it can be transferred. The cooling step is performed with a gas inert to the film formed on the wafer 100 in the reaction chamber 104 (for example, an inert gas supplied from the purge gas supply source 112) so that oxygen is not adsorbed / reacted on the substrate. It may be performed after replacement. If the annealing step S60 is not performed, the cooling step S70 may not be performed.

(Substrate unloading step S80)
After the temperature of the reaction chamber 104 and the wafer 100 is lowered and the wafer 100 can be unloaded, the unloading process of the wafer 100 is performed. Note that hydrogen peroxide may remain in the reaction chamber 104 when the annealing process is not performed. In this case, the wafer 100 is unloaded after the processing liquid removal step described below is performed.

(Processing liquid removal step S90)
The hydrogen peroxide remaining in the reaction chamber 104 may become a gas or a liquid and adhere to members in the reaction chamber 104. This residual gas or liquid may form a water spot on the wafer 100 or corrode a member containing metal that exists outside the reaction chamber 104. Therefore, in this removal step, the inside of the reaction chamber 104 is evacuated to a vacuum by the exhaust part (particularly, the exhaust pump 105b). By evacuating, the hydrogen peroxide that has become liquid is also discharged as a gas. Further, by supplying an inert gas at an arbitrary timing, discharge of hydrogen peroxide may be promoted. For example, by alternately performing vacuum evacuation and inert gas supply, the hydrogen peroxide discharge efficiency is improved.

(Maintenance process S100)
In addition, a maintenance process for cleaning and parts replacement is performed on the processing liquid supply unit 101b as necessary. Since the hydrogen peroxide solution may react with a metal or the like, it is necessary to clean the piping for supplying the treatment liquid before and after maintenance. In the maintenance process, first, the automatic valves 111a and 111b are closed, and the supply of hydrogen peroxide water is stopped. Thereafter, by opening the manual valves 110a and 110b, water containing no impurities such as distilled water is supplied to the pipe from the purge water supply unit 107, and the hydrogen peroxide solution in the treatment liquid supply unit 101b and the vaporization unit 101c is removed. Is done. The water and hydrogen peroxide sent to each part are stored in the drain 101d. Thereafter, purge gas is supplied from the purge air supply unit 108 or the purge gas supply source 112, and water in the processing liquid supply unit 101b and the vaporization unit 101c is removed. The water pushed out by this purge is also stored in the drain 101d. In this manner, parts replacement or the like is performed in a state where the processing liquid in the pipe for supplying the processing liquid is removed. By performing this process, maintenance work can be performed safely.

As mentioned above, although one embodiment of the present invention was described concretely, the present invention is not limited to the above-mentioned embodiment, and can be variously changed without departing from the gist thereof.

<Other Embodiments of the Present Invention>
As mentioned above, although embodiment of this invention was described concretely, this invention is not limited to the above-mentioned embodiment, It can change variously in the range which does not deviate from the summary.

For example, in the above-described embodiment, the case where the wafer 100 coated with polysilazane has been processed has been described. However, the present invention is not limited to such a form, and a wafer or glass substrate with minute irregularities formed on the surface, a minute substrate Wafers coated with polysilazane on unevenness, carbon-containing wafers, and glass substrates can be similarly processed. By treating a substrate having minute irregularities formed on the surface, the irregular surface can be uniformly oxidized. Moreover, the polysilazane in a recessed part can be uniformly oxidized by processing the wafer by which the polysilazane was apply | coated on the micro unevenness | corrugation. Even in the case of a glass substrate, since the processing temperature is equal to or lower than the softening temperature of the glass, the same processing can be performed.

Further, for example, in the above-described embodiment, the case where one dropping nozzle is provided has been described, but the present invention is not limited to such a form, and a plurality of dropping nozzles may be provided to increase the dropping amount. good. By providing a plurality of nozzles, the amount of hydrogen peroxide vapor can be increased. Moreover, by making the droplets small, it is possible to suppress the temperature drop of the vaporization container for each dropping and to generate steam more stably. Furthermore, the droplet of the liquid to be dropped may be further reduced by using the dropping nozzle as a spray nozzle. On the contrary, when the amount of steam is too large or when the temperature of the vaporization container to be heated is drastically reduced, the amount of steam can be adjusted to an appropriate amount by reducing the number of nozzles.

In the above description, the manufacturing process of the semiconductor device has been described. However, the invention according to the above-described embodiment can be applied to processes other than the manufacturing process of the semiconductor device. For example, the present invention can be applied to a sealing process of a substrate having liquid crystal in a manufacturing process of a liquid crystal device and a coating process to a glass substrate, a ceramic substrate, or a plastic substrate used in various devices. Furthermore, it can be applied to a water-repellent coating treatment on a mirror or the like.

In the above description, an example of processing a substrate coated with polysilazane has been described. However, the coating film to be processed is not limited to this, and a coating film made of a material having a silazane bond (Si—N bond) is used. I just need it. For example, it can be applied to a treatment for a coating film using hexamethyldisilazane (HMDS), hexamethylcyclotrisilazane (HMCTS), polycarbosilazane, or polyorganosilazane.

In addition, for example, a substrate on which a silicon-containing film is formed by a CVD method using a silicon raw material such as monosilane (SiH ₄ ) gas or trisilylamine (TSA) gas may be used.

As a method for forming a silicon-containing film by a CVD method, in particular, a flowable CVD (F-CVD) method can be used. By the F-CVD method, for example, a gap having a large aspect ratio is filled with a silicon-containing film, and the filled silicon-containing film can be subjected to oxidation treatment or annealing treatment in the present invention.

<Preferred embodiment of the present invention>
Hereinafter, preferred embodiments of the present invention will be additionally described.

<Appendix 1>
According to one aspect of the invention,
A vaporization container having a carrier gas introduction port and a discharge port;
A dropping nozzle configured to drop a liquid containing two or more substances having different boiling points in the vaporizing vessel into the vaporizing vessel;
A first vaporization surface provided at a position where the liquid is dropped from the dropping nozzle in the vaporization container, and having a horizontal or inclined with respect to the horizontal;
There is provided a vaporization device comprising: a heater that heats the first vaporization surface; and an inclination angle adjustment mechanism that changes an inclination angle of the first vaporization surface.

<Appendix 2>
According to another aspect of the invention,
A vaporization container having a carrier gas introduction port and a discharge port at both ends;
A dropping nozzle configured to drop a liquid containing two or more substances having different boiling points in the vaporizing vessel into the vaporizing vessel;
A first vaporization surface provided at a position where the liquid is dripped from the dropping nozzle in the vaporization container, and having a horizontal or horizontal inclination along a direction from one end to the other end of the vaporization container; ,
A heater for heating the first vaporization surface;
There is provided a vaporizing device having an inclination angle adjusting mechanism for changing an inclination angle of the first vaporization surface.

<Appendix 3>
According to another aspect of the invention,
A vaporization container having a carrier gas introduction port and a discharge port at both ends;
A dropping nozzle configured to drop a liquid containing two or more substances having different boiling points in the vaporizing vessel into the vaporizing vessel;
A first vaporization provided in a position where the liquid is dropped from the dropping nozzle in the vaporization container, and having a slope that is lowered horizontally or horizontally with respect to a direction in which the carrier gas flows from the introduction port to the discharge port. Surface,
A heater for heating the first vaporization surface;
There is provided a vaporizing device having an inclination angle adjusting mechanism for changing an inclination angle of the first vaporization surface.

<Appendix 4>
The vaporizer according to any one of appendices 1 to 3,
A second vaporization surface having an inclination angle different from the inclination angle of the first vaporization surface;
The heater is configured to heat the second vaporized surface;
The inclination angle adjusting mechanism is configured to change an inclination angle of the second vaporization surface.

<Appendix 5>
The vaporizer according to any one of appendices 1 to 3,
An inclination angle that is provided on the downstream side of the first vaporization surface in a direction in which the liquid dropped from the dropping nozzle flows on the first vaporization surface and is different from the inclination angle of the first vaporization surface A second vaporization surface having
The heater is configured to heat the second vaporized surface;
The inclination angle adjusting mechanism is configured to change an inclination angle of the second vaporization surface.

<Appendix 6>
According to another aspect of the invention,
A vaporization container having a carrier gas introduction port and a discharge port at both ends;
A dropping nozzle configured to drop a liquid containing two or more substances having different boiling points in the vaporizing vessel into the vaporizing vessel;
A first vaporization surface provided at a position where the liquid is dripped from the dropping nozzle in the vaporization container, and having a horizontal or horizontal inclination along a direction from one end to the other end of the vaporization container; ,
A second vaporization surface having an inclination angle different from an inclination angle of the first vaporization surface;
A heater for heating the first vaporization surface and the second vaporization surface;
There is provided a vaporizing device having an inclination angle adjusting mechanism that changes an inclination angle of at least one of the first vaporization surface and the second vaporization surface.

<Appendix 7>
According to another aspect of the invention,
A vaporization container having a carrier gas introduction port and a discharge port at both ends;
A dropping nozzle configured to drop a liquid containing two or more substances having different boiling points in the vaporizing vessel into the vaporizing vessel;
A first vaporization provided in a position where the liquid is dropped from the dropping nozzle in the vaporization container, and having a slope that is lowered horizontally or horizontally with respect to a direction in which the carrier gas flows from the introduction port to the discharge port. Surface,
The liquid is provided at a position where the liquid flows through the first vaporization surface, and has an inclination different from an inclination angle of the first vaporization surface in a direction in which the carrier gas flows from the introduction port to the discharge port. A second vaporization surface having an angle; and a heater for heating the first vaporization surface and the second vaporization surface;
There is provided a vaporizing device having an inclination angle adjusting mechanism that changes an inclination angle of at least one of the first vaporization surface and the second vaporization surface.

<Appendix 8>
The vaporizer according to any one of appendix 6 or 7,
In the direction in which the carrier gas flows from the introduction port to the discharge port, the second vaporization surface has an inclination angle that is lower than the horizontal angle smaller than the inclination angle of the first vaporization surface, or is horizontal. Alternatively, it has an inclination that rises relative to the horizontal.

<Appendix 9>
The vaporizer according to any one of appendices 6 to 8,
The tilt angle adjusting mechanism is configured to change the tilt angles of both the first vaporization surface and the second vaporization surface.

<Appendix 10>
The vaporizer according to any one of appendices 6 to 8,
The tilt angle adjusting mechanism is configured to change the tilt angle of the entire vaporization container.

<Appendix 11>
The vaporizer according to any one of appendices 6 to 8,
The inclination angle adjusting mechanism is configured to individually change the inclination angle of the first vaporization surface and the inclination angle of the second vaporization surface.

<Appendix 12>
The vaporizer according to any one of appendices 1 to 11,
A first sensor which is provided at a position where the liquid is dropped from the dropping nozzle and measures the temperature of the first vaporization surface;
A control unit configured to control the output of the heater based on temperature information input from the first sensor.

<Appendix 13>
The vaporizer according to any one of appendices 6 to 8,
The heater is a single heater that heats the first vaporization surface and the second vaporization surface.

<Appendix 14>
The vaporizer according to any one of appendices 6 to 8,
The heater includes a first heater that individually heats the first vaporization surface and a second heater that individually heats the second vaporization surface.

<Appendix 15>
The vaporizer according to any one of appendices 6 to 8,
Based on temperature information input from the first sensor, a heater provided on the first vaporization surface and a controller configured to control an output of the heater provided on the second vaporization surface. .

<Appendix 16>
The vaporizer according to appendix 14, wherein
A first sensor for measuring the temperature of the first vaporization surface provided at a position where the liquid is dripped from the dropping nozzle; and a temperature of the second vaporization surface provided on the second vaporization surface. A second sensor for measuring
The output of the first heater is controlled based on the temperature information input from the first sensor, and the output of the second heater is controlled based on the temperature information input from the second sensor. A control unit configured.

<Appendix 17>
The vaporizer according to any one of appendices 12, 15 or 16,
The controller is configured such that the temperature of the first vaporization surface is lower than the boiling point of the substance having the highest boiling point among two or more substances having different boiling points contained in the liquid, and the liquid The heater is controlled so as to be within a temperature range higher than the boiling point.

<Appendix 18>
The vaporizer according to appendix 17,
The liquid is hydrogen peroxide solution.

<Appendix 19>
The vaporizer according to appendix 18, wherein
Of the two or more substances having different boiling points contained in the liquid, the substance having the highest boiling point is hydrogen peroxide, and the substance having the lowest boiling point is water.

<Appendix 20>
The vaporizer according to appendix 18, wherein
The control unit is configured to control the heater so that the temperature of the first vaporization surface is 150 ° C. or lower.

<Appendix 21>
The vaporizer according to any one of appendices 1 to 20,
A surface parallel to the first vaporization surface, to which a spirit level is attached, is provided outside the vaporization container.

<Appendix 22>
A plurality of vaporizers according to any one of appendices 1 to 21,
There is provided a vaporizer including a single gas discharge port through which gases discharged from the exhaust ports included in each of the plurality of vaporizers merge and are discharged.

<Appendix 23>
The vaporizer according to any one of appendices 1 to 22,
The carrier gas is an oxygen-containing gas.

<Appendix 24>
According to another aspect of the invention,
A reaction chamber for processing the substrate;
A vaporizer that vaporizes a treatment liquid containing two or more substances having different boiling points to generate a treatment gas;
A processing gas introduction nozzle for introducing the processing gas generated by the vaporizer into the reaction chamber;
An exhaust system for exhausting the atmosphere in the reaction chamber,
The vaporizer is
A vaporization container having a carrier gas introduction port and a discharge port at both ends;
A dropping nozzle configured to drop the treatment liquid into the vaporization container in the vaporization container;
A first vaporization surface that is provided in a position where the treatment liquid is dripped from the dropping nozzle in the vaporization vessel and has a horizontal or horizontal inclination along a direction from one end to the other end of the vaporization vessel. When,
A heater for heating the first vaporization surface;
A substrate processing apparatus comprising: an inclination angle adjusting mechanism that changes an inclination angle of the first vaporization surface;

<Appendix 25>
The substrate processing apparatus according to appendix 24, wherein
A treatment liquid supply system for delivering the treatment liquid to the dropping nozzle;
A carrier gas supply system for supplying a carrier gas to the introduction port.

<Appendix 26>
The substrate processing apparatus according to appendix 24 or 25,
A film having a silazane bond is formed on the surface of the substrate to be processed in the reaction chamber.

<Appendix 27>
The substrate processing apparatus according to appendix 26, wherein
The film having a silazane bond is a polysilazane film.

<Appendix 28>
The substrate processing apparatus according to any one of appendices 24 to 26,
A valve provided between a discharge port of the vaporizer and the processing gas introduction nozzle;
The process gas generated by the vaporizer is controlled to be opened to supply the process gas introduction nozzle, and the exhaust system is controlled to stop the exhaust of the atmosphere in the reaction chamber. And a control unit.

<Appendix 29>
According to another aspect of the invention,
Carrying the substrate into a reaction chamber for processing the substrate;
A vaporization container having a carrier gas introduction port and a discharge port at both ends; a dropping nozzle configured to drop a treatment liquid containing two or more substances having different boiling points into the vaporization container; and A first vaporization surface which is provided at a position where the treatment liquid is dripped from the dripping nozzle and has an inclination with respect to a horizontal or horizontal plane along a direction from one end to the other end of the vaporization vessel; and the first The liquid is dripped from a second vaporization surface having an inclination angle different from the inclination angle of the vaporization surface, a heater for heating the first vaporization surface and the second vaporization surface, and the dropping nozzle. A first sensor that measures a temperature of the first vaporization surface, and an inclination angle that changes an inclination angle of at least one of the first vaporization surface and the second vaporization surface. Adjustment mechanism and In vaporizer comprising,
Heating the first vaporization surface and the second vaporization surface by the heater;
The treatment liquid is dropped from the dropping nozzle onto the first vaporization surface, and the temperatures of the first vaporization surface and the second vaporization surface are predetermined based on the temperature acquired from the first sensor. A process of vaporizing the processing liquid by controlling to maintain the temperature and generating a processing gas;
There is provided a method for manufacturing a semiconductor device or a substrate processing method, comprising the step of introducing the processing gas generated in the step of generating the processing gas into the reaction chamber.

<Appendix 30>
According to another aspect of the invention,
A procedure for carrying the substrate into a reaction chamber for processing the substrate;
A vaporization container having a carrier gas introduction port and a discharge port at both ends; a dropping nozzle configured to drop a treatment liquid containing two or more substances having different boiling points into the vaporization container; and A first vaporization surface which is provided at a position where the treatment liquid is dripped from the dripping nozzle and has an inclination with respect to a horizontal or horizontal plane along a direction from one end to the other end of the vaporization vessel; and the first The liquid is dripped from a second vaporization surface having an inclination angle different from the inclination angle of the vaporization surface, a heater for heating the first vaporization surface and the second vaporization surface, and the dropping nozzle. A first sensor that measures a temperature of the first vaporization surface, and an inclination angle that changes an inclination angle of at least one of the first vaporization surface and the second vaporization surface. Adjustment mechanism and In vaporizer comprising,
Heating the first vaporization surface and the second vaporization surface by the heater;
The treatment liquid is dropped from the dropping nozzle onto the first vaporization surface, and the temperatures of the first vaporization surface and the second vaporization surface are predetermined based on the temperature acquired from the first sensor. A procedure of generating a processing gas by controlling the temperature so as to vaporize the processing liquid and maintaining the temperature;
A program for causing a computer to execute a procedure for introducing the processing gas generated in the step of generating the processing gas into the reaction chamber, or a computer-readable recording medium storing the program is provided.

According to the present invention, there is provided a technique capable of improving the manufacturing quality of a semiconductor device and improving the manufacturing throughput.

DESCRIPTION OF SYMBOLS 100 ... Wafer (substrate) 101b ... Processing-liquid supply unit 101c ... Evaporation unit 104 ... Reaction chamber 113 ... Liquid flow control device 114 ... Evaporation device 200 ... Controller 300 ...・ Processing droplet lower nozzle 302... Evaporation tube 303... Evaporation heater 305... Thermocouple 310.

Claims (15)

A vaporization container having a carrier gas introduction port and a discharge port at both ends;
A dropping nozzle configured to drop a liquid containing two or more substances having different boiling points in the vaporizing vessel into the vaporizing vessel;
A first vaporization provided in a position where the liquid is dropped from the dropping nozzle in the vaporization container, and having a slope that is lowered horizontally or horizontally with respect to a direction in which the carrier gas flows from the introduction port to the discharge port. Surface,
A heater for heating the first vaporization surface;
A vaporization apparatus comprising: an inclination angle adjustment mechanism that changes an inclination angle of the first vaporization surface. The vaporizer according to claim 1,
A second vaporization surface having an inclination angle different from the inclination angle of the first vaporization surface;
The heater is configured to heat the second vaporized surface;
The vaporization apparatus configured to change the inclination angle of the second vaporization surface. The vaporizer according to claim 1,
An inclination angle that is provided on the downstream side of the first vaporization surface in a direction in which the liquid dropped from the dropping nozzle flows on the first vaporization surface and is different from the inclination angle of the first vaporization surface A second vaporization surface having
The heater is configured to heat the second vaporized surface;
The vaporization apparatus configured to change the inclination angle of the second vaporization surface. 4. The vaporization apparatus according to claim 3, wherein the second vaporization surface has an angle of inclination with respect to the horizontal in the direction in which the carrier gas flows from the introduction port to the discharge port. Vaporizer having an inclination smaller than the angle of inclination, or horizontal or rising relative to horizontal. A vaporizing device according to claim 3, wherein
The said inclination angle adjustment mechanism is a vaporization apparatus comprised so that the angle of inclination of both the said 1st vaporization surface and the said 2nd vaporization surface may be changed. A vaporizing device according to claim 3, wherein
A first sensor which is provided at a position where the liquid is dropped from the dropping nozzle and measures the temperature of the first vaporization surface;
And a control unit configured to control an output of the heater based on temperature information input from the first sensor. The vaporizer according to claim 6,
The vaporizer is a single heater that heats the first vaporization surface and the second vaporization surface. The vaporizer according to claim 6,
The control unit is configured such that the temperature of the first vaporization surface and the second vaporization surface is lower than the boiling point of the substance having the highest boiling point among two or more substances having different boiling points contained in the liquid. And a vaporizer configured to control the heater so as to be within a temperature range higher than a boiling point of the liquid. A vaporizing device according to claim 8, wherein
The vaporizer wherein the liquid is hydrogen peroxide. The vaporizer according to claim 9, wherein
The said control part is a vaporization apparatus comprised so that the temperature of a said 1st vaporization surface might be controlled to be 150 degrees C or less. The vaporizer according to claim 1,
A vaporization device having a surface parallel to the first vaporization surface on the outside of the vaporization container, to which a level is attached. A plurality of vaporizers according to claim 1,
A vaporizer including a single gas discharge port through which gases discharged from the exhaust ports included in each of the plurality of vaporizers merge and are discharged. A reaction chamber for processing the substrate;
A vaporizer that vaporizes a treatment liquid containing two or more substances having different boiling points to generate a treatment gas;
A processing gas introduction nozzle for introducing the processing gas generated by the vaporizer into the reaction chamber;
An exhaust system for exhausting the atmosphere in the reaction chamber,
The vaporizer is
A vaporization container having a carrier gas introduction port and a discharge port at both ends;
A dropping nozzle configured to drop the treatment liquid into the vaporization container in the vaporization container;
A first vaporization surface that is provided in a position where the treatment liquid is dripped from the dropping nozzle in the vaporization vessel and has a horizontal or horizontal inclination along a direction from one end to the other end of the vaporization vessel. When,
A heater for heating the first vaporization surface;
A substrate processing apparatus comprising: an inclination angle adjusting mechanism that changes an inclination angle of the first vaporization surface. The substrate processing apparatus according to claim 13,
A treatment liquid supply system for sending hydrogen peroxide water as the treatment liquid to the dropping nozzle;
And a carrier gas supply system for supplying an oxygen-containing gas as a carrier gas to the introduction port. Carrying the substrate into a reaction chamber for processing the substrate;
A vaporization container having a carrier gas introduction port and a discharge port at both ends; a dropping nozzle configured to drop a treatment liquid containing two or more substances having different boiling points into the vaporization container; and A first vaporization surface which is provided at a position where the treatment liquid is dripped from the dripping nozzle and has an inclination with respect to a horizontal or horizontal plane along a direction from one end to the other end of the vaporization vessel; and the first The liquid is dripped from a second vaporization surface having an inclination angle different from the inclination angle of the vaporization surface, a heater for heating the first vaporization surface and the second vaporization surface, and the dropping nozzle. A first sensor that measures a temperature of the first vaporization surface, and an inclination angle that changes an inclination angle of at least one of the first vaporization surface and the second vaporization surface. Adjustment mechanism and In vaporizer comprising,
Heating the first vaporization surface and the second vaporization surface by the heater;
The treatment liquid is dropped from the dropping nozzle onto the first vaporization surface, and the temperatures of the first vaporization surface and the second vaporization surface are predetermined based on the temperature acquired from the first sensor. A process of vaporizing the processing liquid by controlling to maintain the temperature and generating a processing gas;
Introducing the processing gas generated in the step of generating the processing gas into the reaction chamber;
A method for manufacturing a semiconductor device comprising:

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