JPH0445837A - Bubbling mechanism and surface-treating device including the mechanism - Google Patents

Abstract

PURPOSE:To increase the area of the interface between a liq. material and a carrier gas and to stably generate an introducing gas at a high flow rate by forming a bubbler vessel for holding a specified liq. with a spiraled pipe member. CONSTITUTION:An airtight bubbler vessel 1 for holding a specified liq. 2 (e.g. tetraethyl orthosilicate) and a carrier gas inlet mechanism 8 for introducing a carrier gas (e.g. gaseous argon) into the vessel 1 are provided, and the liq. 2 is bubbled by the carrier gas and vaporized to generate a gaseous mixture. In this case, the vessel 1 is formed with a spiraled pipe member. Consequently, the temp. of the liq. material is stabilized, the area of the interface between the liq. material and the carrier gas is increased, and an introducing gas is stably generated at a high flow rate.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a bubbling mechanism and a surface treatment device including the same, and in particular to a bubbling mechanism that vaporizes a liquid raw material and a mixed gas generated by the bubbling action of this bubbling mechanism. By using this, it is possible to perform treatments such as film formation, etching, surface cleaning, and surface modification for insulating films, protective films, semiconductor films, metal films, etc. used in sensors, optical components, audio products, semiconductor devices, etc. Surface treatment equipment that performs
Alternatively, the present invention relates to a surface treatment device that performs hardening treatment on the surface of a knife, a cutting tool, or the like.

[Conventional technology]

By activating a gas through a thermochemical reaction or a reaction using active species, a target substance can be deposited on the surface of a substrate to form a thin film, or it can be etched or
Treatment methods for surface cleaning, surface modification, etc. have been rapidly developed in recent years. The gas introduced into the reaction chamber to carry out the above treatment method is not only gaseous, but also often liquid at room temperature and pressure.

Conventionally, the method of vaporizing liquid raw materials and supplying gas into the reaction chamber is the method of heating the liquid, vaporizing it, and transporting it (S
Manufactured by TEC, Liquid 5source Cant
There is a method using a bubbler having a structure as shown in FIG. 9, which heats the liquid in a cylinder and bubbles it with a predetermined carrier gas.

In FIG. 9, 101 is a predetermined liquid raw material, 102 is a container containing the liquid raw material 101, 103 is a pipe for supplying carrier gas, 104 is a flow of carrier gas,
Reference numeral 105 does not indicate the flow of mixed gas generated by bubbling action.

Further, 106 and 107 are valves provided in the supply pipe.

The former supply method enables stable gas introduction by providing a mass flow controller between the cylinder containing the liquid raw material and the reaction chamber.

The latter supply method vaporizes the liquid raw material by bubbling it, and has the advantage that a large flow rate of the raw material can be introduced compared to the above-mentioned supply method that does not perform bubbling.

[Problem to be solved by the invention]

The former method described above, in which a gas is supplied by heating and vaporizing a liquid, has a problem in that it is difficult to introduce a large flow rate of raw materials.

On the other hand, in the latter method of heating bubbling, it is possible to introduce a large flow rate of raw materials, but problems arise due to the bubbling action of the bubbler. That is, due to bubbling, the temperature in the vicinity of where carrier gas bubbles are generated becomes extremely low due to the heat of vaporization. For this reason, especially in the case of commonly used raw materials with poor thermal conductivity, the amount supplied decreases and the amount of gas introduced becomes unstable. Furthermore, because the carrier gas bubbles and the liquid raw material are in contact for a shorter time than it takes to reach saturated vapor pressure, the supply amount is not constant, and it is difficult to ensure a sufficient amount of gas generation. The problem was that I couldn't do it.

In view of the above problems, an object of the present invention is to maintain the temperature of a liquid raw material stably, increase the interface area between the liquid raw material and a carrier gas, and generate a large flow rate of introduced gas in a stable state. The objective is to provide a bubbling mechanism that can.

Another object of the present invention is to provide a surface treatment apparatus that can perform surface treatment of high quality and with good reproducibility by utilizing the bubbling mechanism described in section 2 above.

[Means to solve the problem]

A first bubbling mechanism according to the present invention includes a bubbler container whose interior is kept airtight and stores a predetermined liquid, and a carrier gas introduction mechanism that introduces a carrier gas into the bubbler container, and carries the liquid into the carrier. A bubbling mechanism that generates a mixed gas by bubbling and vaporizing gas is characterized in that the bubbler container is formed of a pipe member processed into a spiral shape.

A second bubbling mechanism according to the present invention includes a bubbler container whose interior is kept airtight and stores a predetermined liquid, and a carrier gas introduction mechanism that introduces a carrier gas into the bubbler container, and carries the liquid into the carrier. A bubbling mechanism that generates a mixed gas by bubbling and vaporizing gas is characterized in that the bubbler container is formed of a pipe member bent at multiple points.

A third bubbling mechanism according to the present invention is characterized in that, in the first or second configuration, a thermal bumper is provided and the bubbler container is assembled to the thermal bumper.

In the fourth bubbling mechanism according to the present invention, in the third configuration, the heat bumper is a block formed of a predetermined metal member having a groove in a shape corresponding to the shape of the bubbler container on the surface; The feature is that the bubbler container is buried in the groove.

The surface treatment apparatus according to the present invention includes a substrate whose surface is subjected to a predetermined treatment, a reaction chamber that houses the substrate, an exhaust device that exhausts the reaction chamber, and a temperature adjustment mechanism that adjusts the temperature of the substrate. The bubbling mechanism described in any one of the first to fourth items is included for vaporizing and introducing a predetermined liquid into the reaction chamber.

[Effect]

In the first and second bubbling mechanisms according to the present invention, the diameter of the bubbler container is made small by making it from a pipe member, and the temperature change of the liquid raw material contained therein is reduced and stabilized, and Increase the length of the bubbler container to increase the contact time between the carrier gas and the liquid raw material,
In other words, by increasing the interfacial area, vaporization is effectively performed, the bubbling effect is stabilized, and a stable large flow rate of introduced gas is generated.

In the third and fourth bubbling mechanisms according to the present invention, in addition to the above-mentioned effects, by providing an optimal thermal bumper corresponding to the shape of the bubbler container and maintaining the bubbler container at an appropriate temperature, The temperature state of the liquid raw material is further stabilized, and the supply amount of the introduced gas is further stabilized.

In the surface treatment apparatus according to the present invention, a large and stable flow rate of raw material gas is introduced into the reaction chamber by the bubbling mechanism that produces the above-mentioned effect, and effective surface treatment is performed.

〔Example〕

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

An embodiment of the bubbling mechanism according to the present invention will be described based on FIG. In FIG. 1] is a bubbler container, and this bubbler container 1 is formed by spirally winding a pipe made of SUS and having a predetermined diameter (for example, 1 inch). The inside of the bubbler container 1 is filled with tetraethyl orthosilicate (hereinafter abbreviated as TE01) 2. Note that tetraethoxysilane can also be used as the filling liquid instead of TE01. The bubbler container 1 is placed underwater in a thermos flask 4 containing water 3.

A solution reservoir 5 is formed at the upper end of the bubbler container 1 in a position outside the water 3, and a 1/4 inch vibro is connected to the tip of the solution reservoir 5. A valve 7 is provided in the middle of the vibro, and the other end is connected to a reaction chamber (not shown).

The solution reservoir 5 mentioned above is provided to prevent TEO 82 from being supplied as a liquid to the reaction chamber. Meanwhile, the lower end of the bubbler container is connected to a 174-inch pipe 8. The pipe 8 is drawn out to the outside of the water 3, and a valve 9 is disposed in the middle. The other end of the pipe 8 is connected to a carrier gas generator (not shown).

Further, a heater 10 is disposed at a predetermined position in the water 3 of the thermos 4, and the water 3 is heated by the heater 10. 11 is a magnetic stirrer, and this magnetic stirrer 11 generates a magnet 1□ 1-1. A is rotated to measure the temperature of the water 3 with a thermocouple 12 while stirring the water 3.

Based on the water temperature measured by the thermocouple 12, a bubbling temperature adjustment mechanism (not shown) performs PID control, PI control, 0
Heater 10 using N-OFF control, fuzzy control, etc.
The water 3 is maintained at the required temperature.

In the above configuration, when the carrier gas (argon gas) is supplied from the carrier gas generator using the pipe 8 as shown by the arrow 13 with the valves 7 and 9 open, the TEO 32 is heated in the spiral bubbler container 1-. bubbling is performed. When bubbling is performed in the bubbler container 1 in this way, based on the spiral shape of the pipe member of the bubbler container 1 and its temperature control, as explained in the operation section, the TEO 82 is effectively vaporized at a constant temperature. A mixture of argon gas moves in the direction of arrow 14 at a high and stable flow rate and is supplied to the reaction chamber via valve 7 through the vibro.

Next, another embodiment of the bubbling mechanism will be described based on FIG. In FIG. 2, the same components as in FIG. 1 are designated by the same reference numerals, and their explanations will be omitted.

In this example, regarding the shape of the bubbler container, reference numeral 21 is used.
As shown in the figure, one piece of pipe made of SUS is
A bubbler container is used that is bent into a continuous dogleg shape, hairpin shape, or zigzag shape. The other configurations are basically the same as the configuration of the embodiment shown in FIG. Therefore, in addition to the functions and effects described in the embodiment of FIG. 1, the three-dimensional shape of the bubbler container as a whole becomes thinner, and there is an advantage that it takes up less space in the interior space of the thermos flask 4. In this embodiment, the solution reservoir 5 is not installed, but even with such a configuration, the same gas supply as in the embodiment shown in FIG. 1 is possible.

Next, another embodiment of the bubbling mechanism will be described based on FIG. In FIG. 3, the same components as in FIG. 1 are denoted by the same reference numerals 1, and their explanations will be omitted. In this embodiment, a bubbler container 1 made of a 1-inch pipe made of SUS is arranged in a copper block 31 which is formed into a cylindrical shape and has a spiral groove 31a formed on its outer circumferential surface. It is assembled so as to be wrapped around the groove 31a.

The gap between the bubbler container 1 and the block 31 is filled with brazing or soldering. Third
In the figure, the upper side of the block 31 is shown as a front view, and the lower side is shown as a longitudinal sectional view. The assembly of the copper block 31 and the bubbler container 1 is heated by a mantle heater 32 having the same function as the heater 10 arranged around it. Block 31 acts as a thermal bumper. All of the mantle heaters 32 are shown with diagonal lines in FIG. In this example, a bathtub and water are not used. Further, the thermocouple 12 is sandwiched between the bubbler container 1 and the mantle heater 32.

FIG. 4 shows another embodiment of the bubbling mechanism. In this embodiment, a bubbler container 21 having the shape shown in FIG. It is configured to be embedded along the groove of the copper plate 41. If there is a gap between the blanker container 21 and the copper plate 41, the gap is filled in the same way as in the embodiment described above. The other configurations are basically the same as those shown in FIG. 3. In this embodiment, a solution reservoir 5 is provided.

The modified embodiments shown in FIGS. 3 and 4 described above can also produce the same bubbling effect as the embodiments shown in FIGS. 1 and 2 described above. It is also convenient to handle because it does not require a thermos flask or water.

Another embodiment shown in FIG. 5 is a further modification of the embodiment shown in FIG. In this embodiment, another spiral groove 31b is formed on the outer peripheral surface between the spiral bubbler containers 1 in the block 31, and a 1/2 inch pipe 51 made of SUS is inserted into the groove 31. It is configured to be embedded in b.

Then, heated water from the constant temperature bath 54 is circulated through the pipe 51 in the directions shown by arrows 52 and 53 using a pump, and the T in the pipe 1 is
Heat EO82. As a result, the same functions and effects as in each of the above-mentioned embodiments can be achieved. Further, when the surface treatment is completed, a chiller 55 is used to circulate cooling water through the pipe 51 in order to quickly reduce thermal decomposition of the TEO 32. 56 is a valve for switching between the constant temperature bath 54 and the chiller 55. The switching operation of the valve 56 is appropriately controlled by a control device (not shown).

Next, an example of a surface treatment apparatus configured by applying any one of the bubbling mechanisms according to the present invention described above will be described.

FIG. 6 shows a first embodiment of the surface treatment apparatus.

This example shows a method of activating only 02 using high-temperature equilibrium or non-equilibrium plasma, reacting active oxygen with 1' EO8, and coating a substrate with an SO7 film. In FIG. 6, 61 is a discharge chamber, and 62 is a reaction chamber. The discharge chamber 61 is a high frequency (several KH2 to several hundred MH2)
), a switch 64 , a coil 65 , and a discharge tube 66 A discharge occurs. switch 64
Accordingly, one end of the coil 65 can be selected and grounded. O2, which serves as a discharge gas and a reaction gas, is introduced into the discharge tube 66 from the direction shown by an arrow 68 via a valve 69.

The discharge tube 66 is normally made of an insulator, and in this embodiment, quartz glass was used for the discharge tube. Since the quartz glass may melt due to the high temperature of the discharge plasma, the discharge tube 66 is formed as a double tube using quartz glass, and the configuration is such that cooling water flows between the inner tube and the outer tube. are doing.

In the reaction chamber 62 , a substrate 70 is subjected to a predetermined surface treatment, and this substrate 70 is held by a substrate holder 71 . The base boulder 71 has a built-in structure that can adjust the temperature of the base 70 as necessary.

72 is a heater installed inside the base holder 71. Reference numeral 73 indicates the direction of exhaust air from the reaction chamber 62, and the interior of the reaction chamber 62 is evacuated through a valve 74 by a vacuum exhaust system (not shown). Note that 75 is a reaction chamber housing for isolating the reaction chamber 62 from the atmosphere.

76 indicates the flow direction of the reaction gas, and argon gas from the carrier gas cylinder 77 is connected to the mass flow meter 78,
The gas is introduced into the reaction chamber 62 through the valve 9, the bubbler container 79 according to any of the embodiments described above, the valve 7, and a small hole made in the gas introduction ring 80.

High temperature equilibrium or non-equilibrium plasma 81 in discharge chamber 61
The activated species flow from the discharge chamber 61 toward the reaction chamber 62 and are introduced into the reaction chamber 62.

Comparing the surface treatment apparatus with the above configuration and the surface treatment apparatus equipped with a conventional bubbler container (for example, φ150 x 300 mm), it is found that the pressure during film formation in the reaction chamber 62 is Q, 7 Tor+, and the bubbler. Set the temperature of the container to 5
A surface treatment was attempted in which a film of Sin was deposited on a Si substrate at 5° C. for 1 minute. the result,
The thickness of the thin film formed was 8,000 people using conventional equipment;
In the apparatus of the present invention, the number of coats was +8,000, resulting in a difference in film thickness that was twice as large. This means that according to the bubbler container according to the present invention, the moving distance of argon gas as a carrier gas during bubbling becomes longer, and the argon and TE
Because the contact time with 01 is long and the interface area is sufficient, it can be effectively vaporized under specified temperature conditions, and the amount of raw material gas supplied can be stably increased compared to conventional equipment. This is thought to be due to the ability to

FIG. 7 shows a second embodiment of the surface treatment apparatus.

This example shows an apparatus configuration in which 03 is reacted with TE01. An arrow 91 indicates the direction in which 03 is supplied, and 03 is supplied by an ozonizer (not shown). Reaction chamber 6
2 is introduced into the reaction chamber 62 through a small hole made in the gas blowing plate 92. The rest of the structure is the same as that of the embodiment shown in FIG. 6, so the same parts are given the same reference numerals and the explanation thereof will be omitted. Therefore, the bubbling mechanism is the same as in the embodiment shown in FIG. 6, and TE01 is introduced from the gas introduction ring 80, and this TE01 is caused to react with the above-mentioned 03 gas in the reaction chamber 62.

In the case of the apparatus configuration in which 03 and TE01 are reacted as described above, the reaction is slow and the deposition rate on the surface of the substrate 70 is 2000%.
It must be 1 person/m1nL. Therefore, stability is required for the supply of TE01 by the bubbling mechanism.

FIG. 8 shows a graph of pressure fluctuations in the reaction chamber after the start of bubbling, comparing the apparatus of the present invention shown in FIG. 7 with a conventional apparatus equipped with a conventional bubbling mechanism. According to this graph, in a conventional device using a conventional bubbling mechanism, due to the poor thermal conductivity of TE01, the temperature in the vicinity of where bubbles appear due to the heat of vaporization due to bubbling drops extremely, reducing the supply amount. I understand. On the other hand, in the device equipped with the bubbler container according to the present invention, it can be confirmed that the bubbler is stably supplied up to around lomin.

Other application examples of the bubbling mechanism and surface treatment apparatus according to the present invention are not limited to those using a discharge space. Even when triisobutylaluminum or dimethylaluminum hydride is used as the liquid raw material, an aluminum film can be stably produced on the surface of the substrate. Further, when tungsten hexafluoride is used as the liquid raw material, a tungsten film can be produced. Furthermore, when carbon tetrachloride is used as the liquid raw material, stable dry etching becomes possible.

〔Effect of the invention〕

As is clear from the above description, the present invention provides the following effects.

In the bubbling mechanism, the bubbler container is made into a spiral shape or a shape bent at multiple points so that the moving distance of the carrier gas in the liquid raw material is increased by the pipe member, which increases the interfacial area and stabilizes the large flow rate of the raw material gas. It can occur in any situation. Furthermore, a thermal pump is provided around the bubbler container to maintain the optimum temperature condition of the liquid raw material inside the bubbler container, further increasing the stable supply of large flow rate raw material gas through bubbling. Further, in the surface treatment apparatus equipped with the bubbling mechanism according to the present invention, a large flow rate of raw material gas is stably supplied, so that surface treatment with good reproducibility can be performed.

[Brief explanation of drawings]

FIG. 1 is a block diagram showing a first embodiment of the bubbling mechanism according to the present invention, FIGS. 2 to 5 are block diagrams of other embodiments of the bubbling mechanism, and FIG. 6 is a surface treatment apparatus according to the present invention. 1st of
FIG. 7 is a block diagram showing another embodiment of the surface treatment apparatus, and FIG. 8 is a block diagram showing the surface treatment apparatus according to the present invention shown in FIG. 7 and a conventional apparatus. graph,
FIG. 9 is a longitudinal sectional view for explaining a conventional bubbling mechanism. [Explanation of symbols] 1.21.79...Bubbler container 2...TE01 (Liquid raw material) 4...
...Thermos flask 5...Solution reservoir 10...Heater 31.41...Block (thermal bumper) 31a, 41
a... Groove 32... Mantle heater 12... Thermocouple 61... Discharge chamber 62... Reaction chamber 70... ...Gas 71... Gas holder applicant Nichiden Anelva Co., Ltd. agent Patent attorney Hiroki Tamiya

Claims (5)

[Claims] (1) It has a bubbler container whose interior is kept airtight and stores a predetermined liquid, and a carrier gas introduction mechanism that introduces a carrier gas into the bubbler container, and bubbles the liquid with the carrier gas to vaporize it. In the bubbling mechanism that generates a mixed gas, the bubbler container includes:
A bubbling mechanism characterized by being formed of a pipe member processed into a spiral shape. (2) It has a bubbler container whose interior is kept airtight and stores a predetermined liquid, and a carrier gas introduction mechanism that introduces a carrier gas into the bubbler container, and bubbles the liquid with the carrier gas to vaporize it. In the bubbling mechanism that generates a mixed gas, the bubbler container includes:
A bubbling mechanism characterized by being formed from a pipe member that is bent at multiple points. (3) The bubbling mechanism according to claim 1 or 2, wherein a thermal bumper is provided, and the bubbler container is assembled to the thermal bumper. (4) In the bubbling mechanism according to claim 3, the heat bumper is a block formed of a predetermined metal member having a groove on its surface having a shape corresponding to the shape of the bubbler container, and the groove of the block A bubbling mechanism characterized in that the bubbler container is buried. (5) a substrate whose surface is subjected to a predetermined treatment, a reaction chamber that accommodates the substrate, and an exhaust device that exhausts the reaction chamber;
A temperature adjustment mechanism for adjusting the temperature of the substrate, and a bubbling mechanism according to any one of claims 1 to 4 for vaporizing and introducing a predetermined liquid into the reaction chamber. Characteristic surface treatment equipment.