Source: https://patents.google.com/patent/JP4828918B2/en
Timestamp: 2020-01-22 18:49:01
Document Index: 209722975

Matched Legal Cases: ['Art 1', 'art 2', 'art 3', 'art 1', 'art 2', 'art 3', 'art 1', 'art 2', 'art 3']

JP4828918B2 - Vaporizer and vapor phase growth apparatus - Google Patents
Vaporizer and vapor phase growth apparatus Download PDF
JP4828918B2
JP4828918B2 JP2005322412A JP2005322412A JP4828918B2 JP 4828918 B2 JP4828918 B2 JP 4828918B2 JP 2005322412 A JP2005322412 A JP 2005322412A JP 2005322412 A JP2005322412 A JP 2005322412A JP 4828918 B2 JP4828918 B2 JP 4828918B2
JP2005322412A
JP2007129152A (en
芳健 加藤
2005-11-07 Application filed by ルネサスエレクトロニクス株式会社 filed Critical ルネサスエレクトロニクス株式会社
2005-11-07 Priority to JP2005322412A priority Critical patent/JP4828918B2/en
2007-05-24 Publication of JP2007129152A publication Critical patent/JP2007129152A/en
2011-11-30 Publication of JP4828918B2 publication Critical patent/JP4828918B2/en
The present invention relates to a vaporizer and a vapor deposition apparatus for vaporizing a film forming material and supplying it to a chamber.
FIG. 6 shows an example of a conventional vaporizer 30. The vaporizer 30 is an apparatus that vaporizes and supplies a source gas for film formation by CVD (chemical vapor deposition), ALD (atomic layer growth), or the like. In this vaporizer, the liquid raw material is supplied from the raw material pipe 20a, and the supplied raw material is misted by the carrier gas supplied from the carrier gas pipe 36. The mist is gasified in the vaporization space 132 and supplied from the processing gas pipe 40 to the film forming apparatus. (Patent Document 1: Prior Art 1)
Although various types of vaporizers are described in Patent Literature 2, these vaporizers perform gasification on the entire inner wall of the vaporization space. (Prior art 2)
Patent Document 3 discloses a vaporizer configured to retain a liquid raw material when the vaporized raw material flows down. (Prior art 3)
JP2005-39120 JP2005-109349 JP2001-11634
However, in the vaporizer of the type shown in the above-mentioned patent document, a problem that the mist is taken into the grown thin film and the quality of the film is deteriorated often occurs. As a result of the inventor's investigation of the cause, it was presumed that the reason was as follows.
That is, in the conventional vaporizer, after the mist is supplied, it is vaporized after reaching the main vaporization surface 155 which is the bottom in the vaporization space. The inventor of the present application presumed that the flow in which the mist is vaporized is a path indicated by 156 in FIG. At this time, a part of the mist that should have been vaporized on the main vaporization surface 155 is not discharged together with the carrier gas, but is diffused on the vaporizer side wall 158 from the main vaporization surface 155 to the discharge port 139. From the various results, it was found that it would be more appropriate to think that it would be discharged to the device side.
The vaporizer of the present invention has a main vaporization surface facing the strike supply port, the vaporization space, and the mist supply port, and a vaporization device provided with a discharge port provided on a side wall connecting the mist supply port and the main vaporization surface. a vessel, is characterized in that the tip end direction of the main vaporizing surface on the side wall between the main vaporizing surface and the discharge port to prevent surface diffusion of the mist by providing the projections countercurrent memorial.
Generation of mist from the vaporizer can be prevented by using the vaporizer of the present invention. For this reason, the gas phase growth apparatus which can form the film | membrane which does not contain mist is provided. As a result, a high quality film can be stably produced.
FIG. 1 shows a vapor phase growth apparatus 100 according to Embodiment 1 of the present invention. The vapor phase growth apparatus 100 according to this embodiment includes a film forming chamber 26, a gas supply system 110 that introduces a film forming gas into the film forming chamber 26, and an exhaust system 27 that exhausts gas from the film forming chamber 26.
The film forming chamber 26 includes a shower head 21 having a film forming gas supply hole 22 and a wafer holder 24 having a heater 25. Film formation on the wafer 23 is performed in the film formation chamber 26. The wafer 23 is placed on the wafer holder 24 heated by the heater 25. The source gas is supplied from the gas supply system 110 to the shower head 22 and is supplied from here to the heated wafer 23 to grow a thin film. At this time, the pressure in the chamber 26 is appropriately controlled by the exhaust system 27.
The gas supply system 110 to the film forming chamber 26 includes a system that supplies gas from the vaporizer 30 through the pipe 40 and a system that supplies gas 12 from the pipe 10 without passing through the vaporizer. When the gas is introduced from the pipes 40 and 10, the gas supply can be controlled by the pressure control devices 6 and 7 and the valves 8 and 9, respectively. In the case of using a plurality of source gases, the gas supply system 110 can be provided with source supply pipes in addition to the pipes 10 and 40.
The liquid source is pumped to the vaporizer 30 from the liquid source supply source 20 through the liquid source gas pipe 20a, and the supply amount is controlled by the valve 35a. Carrier gas is supplied from the carrier gas pipe 36, and the supply amount is controlled by a valve 37. Here, a liquid raw material is stored in the liquid raw material supply source 20, and the liquid raw material may or may not be diluted.
FIG. 2 shows an enlarged view of the vaporizer 30 of the present embodiment. In the vaporizer 30, the liquid source is supplied from the liquid source gas pipe 20 a and dropped into the mist supply port 57 through the pipe 35 while controlling the amount of the source supplied by the valve 35 a. On the other hand, the carrier gas is supplied from the carrier gas pipe 36 to the mist supply port 57, whereby mist is generated and supplied to the vaporization space 32.
The vaporization space 32 is heated by installing heaters 31, 33, and 34. Here, these heater temperatures are preferably such that the heater 31 = 33 <34, and it is preferable that the temperature gradually increases from the mist supply port 57 to the heater 34 below the mist supply port 57. By performing such temperature setting, it is possible to vaporize while preventing decomposition of the raw material when it is misted.
The mist supplied from the mist supply port 57 reaches the main vaporization surface 55 where the temperature is highest in the vaporization space. The main vaporization surface 55 only needs to face the mist supply port 57, and in this embodiment, the case where it exists in a lower surface is demonstrated as an example. The liquid source gas vaporized on the main vaporization surface 55 is supplied from the exhaust port 39 through the pipe 40 to the film forming chamber 26.
Ideally, all mist is vaporized on the main vaporization surface 55. However, mist that is not vaporized actually remains. On the side wall 58 of the vaporization space 32, a protrusion 42 is provided on the entire surface between the main vaporization surface 55 and the discharge port 39. The protrusions 42 are provided along the circumference of the vaporization space, and are formed on a plane perpendicular to the flow direction of the vaporized liquid source gas. Here, the distance 59 between the side wall 58 and the tip of the protrusion 42 is 2 mm, for example, and the distance 60 is also 2 mm, for example. The mist remaining without being vaporized is prevented from moving to the discharge port by the projection 42. The shape, height, and interval of the protrusions 42 are examples, and can be appropriately set according to the shape of the vaporizer. In addition, it is preferable that the protrusions 42 are provided along the circumference instead of the spiral shape in terms of preventing the movement of mist.
Here, when the interval 60 is set so as not to be 0 mm, the side wall 58 is constituted by a portion where the protrusion and the side wall surface are exposed. When the interval 60 is set to 0 mm, a side wall shape such as 42 'is obtained. When the protrusion has a shape of 42, the presence of a portion where the side wall surface is exposed, an extra corner 61 is formed between the protrusion and the side wall as compared with 42 ', so that the movement of the mist is more easily prevented.
Further, the number of protrusions 42 provided on the side wall can be changed in the vicinity of the main vaporization surface 55 and in the vicinity of the discharge port 39. To change the number of protrusions 42 depending on the location, for example, the interval 60 may be changed depending on the location. By increasing the number of the protrusions 42 in the vicinity of the main vaporization surface 55, it is possible to promote that the mist whose surface diffusion is prevented is vaporized in the vicinity of the main vaporization surface 55 having a higher temperature.
The tip of the protrusion provided on the side wall 58 needs to face the direction of the main vaporization surface 55 as indicated by the protrusion 42. This is because the size of the mist is about 0.1 to 0.5 μm and the surface diffusion cannot be prevented if it is a simple unevenness in which the direction of the tip of the protrusion is not considered. Such movement can be prevented because the tip of the projection faces the direction of the main vaporization surface 55. Another example of the shape of the protrusion is shown in FIG. The protrusion shapes 43 and 44 are more preferable than the protrusion shape 42 because they are more directed to the main vaporization surface side, so that the effect of preventing mist diffusion is increased. The shapes of these protrusions do not have to be the same size, and may be provided so as to gradually change in size toward the discharge port 39.
In this way, since the mist is prevented from being discharged from the discharge port 39, only the vaporized liquid source gas is supplied from the discharge port 39 to the film forming chamber 26. The deposition chamber 26 is supplied with a vaporized liquid source gas that does not contain mist and other source gases, and as a result, a thin film that does not contain mist can be stably formed.
The liquid raw material which vaporizes with the vaporizer 30 of this embodiment is mainly an organometallic raw material. Here, for example, a high-k film is formed by the vapor phase growth apparatus 100 using the vaporizer 30. The high-k film includes a ZrO2 film and an HfO2 film. If the ZrO2 film is used, a liquid source gas obtained by vaporizing a Zr-based liquid source such as TEMAZ (TetraEthylMethylAminoZirconium) or TDAZ (Tetradiethylaminozirconium) from the pipe 40 with the vaporizer 30 is used. The film is formed by supplying an oxygen-based gas from the pipe 10. Further, an HfO 2 film can be formed by using an Hf-based gas such as TEMAH (TetraEthylMethylAminoHafnium) or TDEAH (Tetradiethylaminohafnium) instead. Other organometallic compounds can be used as the Hf or Zr-based liquid source gas, and a silicate film can be formed by using a source gas containing Si.
Here, when TEMAZ is used as the liquid raw material, for example, the heaters 31 and 33 are set to 100 ° C. and 34 is set to 160 ° C. By setting such a temperature, the temperature at the mist supply port is about 60-80 ° C., the temperature near the discharge port 39 is about 100-140 ° C., and the temperature at the main vaporization surface 55 is about 140-160 ° C. It has become. Further, the temperature of the side wall 58 from the exhaust port 39 to the main vaporization surface 55 is gradually increased. By gradually changing the temperature at the side wall, thermal decomposition and liquefaction at a specific location are prevented.
Thus, by accurately controlling the temperature of the inner wall of the vaporization space by the heaters 31, 33, and 34, the liquid raw material is supplied from the mist supply port 57 and then gasified at the main vaporization surface 55 and reaches the discharge port 39. The flow can be controlled. Since this control is performed and the protrusions 42 are further provided, generation of mist can be effectively suppressed, and a High-k film containing no mist is stably formed. Such an effect is particularly effective when using a liquid raw material having a low vapor pressure and characteristics close to the vaporization temperature and the decomposition temperature.
Next, the effect in this embodiment is demonstrated. The mist supplied from the mist supply port 57 is vaporized at the main vaporization surface 55 and supplied from the discharge port 39 through the pipe 40 to the film forming chamber 26 as a liquid source gas. In this case, the mist that was not vaporized was discharged from the discharge port 39 through the surface diffusion of the side wall 58 in the vaporizer shown in the prior art 1. On the other hand, in the present invention, since the projections 42 whose front ends are directed to the main vaporization surface direction are provided on the side wall 58, the surface diffusion of mist is prevented. Thereby, generation | occurrence | production of the mist from a vaporizer is prevented and the thin film which does not contain mist is manufactured stably.
Until now, it has been generally considered that mist is generated by being directly discharged from the mist supply port 57 to the discharge port 39. However, the inventor of the present application has newly noticed that the number of mists contained in the thin film formed by the vaporizer is different even when the same mist supply condition is used with the same vaporizer. If the mist is directly discharged from the mist supply port 57 together with the carrier gas to the discharge port 39, it is considered that a certain mist is always included in the thin film. Therefore, it is considered that the mist is discharged from the discharge port 39 after being diffused on the side wall 58. The present application has been made based on such considerations.
In the vaporizer shown in the prior art 2, the entire vaporization space is controlled at a constant temperature, and all inner walls in the vaporization space are vaporized surfaces. The entire vaporization surface is provided with irregularities that do not consider the mist discharge direction. For this reason, the mist is discharged from the discharge port without being blocked by these irregularities. For this reason, a filter for preventing mist discharge is required at the discharge port. Such a filter causes particle generation due to clogging and the like, making it difficult to stably produce a thin film.
The vaporizer shown in the prior art 3 is also provided with irregularities on the vaporization surface without considering the vaporization surface and the discharge direction of the mist. For this reason, the mist diffuses on the vaporized surface and is easily discharged from the discharge port. On the other hand, in this invention, since the protrusion was provided with the tip facing the main vaporization surface direction in the vaporization space, it is possible to effectively prevent the surface diffusion of mist. For this reason, the thin film which does not contain mist compared with these prior arts can be manufactured stably.
The second embodiment is different in that the vaporizer 30 shown in FIG. 4 is used in the vapor phase growth apparatus 100 similar to the first embodiment. Further, in the carburetor 30 shown in FIG. 4, the projections are not formed on the entire side wall 58 compared to the carburetor 30 shown in FIG. 1, and the projection 45 is formed in a part between the main vaporization surface 55 and the discharge port 39. The difference is that it is formed. Here, the main vaporization surface 55 should just oppose the mist supply port 57, and what was in the lower surface was shown as an example in this embodiment.
As shown in FIG. 4, the mist is prevented from spreading only by providing the protrusion 45 on a part of the side wall 58. Also in this embodiment, since the protrusion 45 whose tip is directed to the main vaporization surface direction in the vaporization space is provided, the surface diffusion of mist can be effectively prevented. For this reason, it is possible to stably form a thin film that does not contain mist as compared with the prior art.
When the projection 45 for preventing mist diffusion is partially provided as in the second embodiment, the processing of the inner wall of the vaporization space is simplified when the vaporizer 30 is manufactured. For this reason, the variation between individuals of the vaporizer 30 is eliminated. Use of such a vaporizer leads to an improvement in stability during thin film formation. Further, the projection 45 may be a projection having another shape as shown in FIG. 3 as long as the tip is directed to the main vaporization surface 55.
In the present embodiment, the protrusion 45 is provided in a portion close to the discharge port of the side wall 58, but it is not limited to this location. Even if the protrusion 45 is closer to the main vaporization surface 55 than the discharge port 39, the desired effect can be obtained if the tip is directed to the main vaporization surface 55. Here, it is more preferable that the protrusion 45 is provided in the vicinity of the main vaporization surface 55. This is because the temperature is higher in the vicinity of the main vaporization surface 55 and the vaporization of the mist that is prevented from surface diffusion is more likely to occur. For the purpose of completely preventing mist discharge, it is most preferable to provide a protrusion on the entire surface from the main vaporization surface 55 to the discharge port 39 as shown in the first embodiment.
The third embodiment is different in that the vaporizer 30 shown in FIG. 5 is used in the vapor phase growth apparatus 100 similar to the first embodiment. Here, the vaporizer 30 shown in FIG. 5 is different in the shape of the side wall portion 59 of the vaporization space 32 from the vaporizer 30 shown in FIG. By using the side wall 59 as shown in FIG. 5, the area of the main vaporization surface 55 increases. For this reason, vaporization efficiency improves and it contributes to the improvement of stability at the time of thin film formation. In the present embodiment, the side wall 59 is shown as an example of another shape, but other side wall shapes such as a curved shape may be used. Further, the shape of the protrusion 46 may be another shape in which the tip of the protrusion is directed more toward the main vaporization surface as shown in FIG. Here, the main vaporization surface 55 should just oppose the mist supply port 57, and what was in the lower surface was shown as an example in this embodiment.
As mentioned above, although the structure of this invention was demonstrated, what combined these structures arbitrarily is effective as an aspect of this invention.
A thin film was grown using the vaporizer 30 of FIG. 2 in the vapor phase growth apparatus 100 shown in the first embodiment. A ZrO 2 thin film of 10 nm was grown on a silicon wafer by ALD using TEMAZ as a liquid raw material and oxygen as an oxidizing agent. At this time, the number of mist adhered on the silicon wafer was examined with a particle counter, and the shape was examined with a surface SEM. As a result, no mist was found on the silicon wafer.
100 pieces of the ZrO 2 thin film of Example 1 were grown on the silicon wafer, and the number of mists adhered on the silicon wafer was observed. As a result, no mist was found on the silicon wafer even after the growth of 100 sheets.
A thin film was grown on the vapor phase growth apparatus 100 shown in FIG. 1 using the vaporizer 30 of the conventional type shown in FIG. The raw materials used and the growth conditions were the same as in Example 1. At this time, as a result of examining the number of mists adhering on the silicon wafer, about 100 to 1000 mists were found on the silicon wafer.
Vapor phase growth apparatus according to Embodiment 1 The vaporizer concerning Embodiment 1 Example of the shape of the protrusion according to the first, second, and third embodiments The vaporizer concerning Embodiment 2 The vaporizer concerning Embodiment 3 Vaporizer according to prior art 1 Vaporizer related to prior art 2 Vaporizer according to prior art 3
DESCRIPTION OF SYMBOLS 100 Vapor growth apparatus 30 Vaporizer 20 Liquid source supply source 26 Film formation chamber 20a Liquid source gas supply piping 23 Wafer 27 Exhaust system 32 Evaporation space 36 Carrier gas supply piping 39 Outlet 42-46 Protrusion 55 Main vaporization surface 57 Mist supply Port 58 Side wall 132 Conventional vaporization space 139 Conventional discharge port 155 Conventional main vaporization surface 156 Mist flow 158 Conventional sidewall 241 Spray port 241a of Conventional Example 2 First vaporization surface 242a of Conventional Example 2 Conventional Example 2 The second vaporization surface 242S of the conventional example 2 The vaporization space 243 of the conventional example 2 The discharge port 244 of the conventional example 2 Filter 308 The raw material supply pipe 315 of the conventional example 3 The vaporization surface 316 of the conventional example 3 The vaporization surface 318 of the conventional example 3 The exhaust of the conventional example 3 Outlet 408 Carrier gas piping V of Conventional Example 3 Vaporization space of Conventional Example 3
A carburetor comprising: a mist supply port; a vaporization space; a main vaporization surface facing the mist supply port; and a discharge port provided in a side wall connecting the mist supply port and the main vaporization surface. ,
Vaporizer tip in the direction of the main vaporizing surface on the side wall between the outlet and the main vaporizing surface and providing a protrusion in direction memorial.
The vaporizer according to claim 1, wherein the protrusion is provided along a circumference.
The vaporizer of claim 1 or 2, characterized in that the projection is provided with a gap so that the side wall is exposed.
Vaporizer as claimed in any one of claims 1 to 3, characterized in that the projection is provided on the entire surface between the outlet and the main vaporizing surface.
Vaporizer as claimed in any one of claims 1 to 4 carbon of the projections is equal to or greater in the main vaporizing surface vicinity than in the vicinity the outlet.
Carburetor according to any one of claims 1 to 5, characterized in that said side wall is cylindrical.
Vaporizer as claimed in any one of claims 1 to 6, wherein the mist supply port with a liquid material supply pipe and the carrier gas supply pipe.
Vaporizer as claimed in any one of claims 1 to 7, characterized in that the temperature of the main vaporizing surface is controlled to be higher than the temperature of the mist supply port.
Vaporizer as claimed in any one of claims 1 to 8, characterized in that the temperature is controlled to be gradually increased in toward the main vaporizing surface from the mist supply port of the vaporizing space.
Vaporizer as claimed in any one of claims 1 to 9, characterized in that said liquid material is a metal organic compound.
Vapor deposition apparatus using a vaporizer as claimed in any one of claims 1 to 10.
12. The vapor phase growth apparatus according to claim 11, wherein an oxide-based thin film containing zirconium or hafnium is grown.
JP2005322412A 2005-11-07 2005-11-07 Vaporizer and vapor phase growth apparatus Expired - Fee Related JP4828918B2 (en)
JP2005322412A JP4828918B2 (en) 2005-11-07 2005-11-07 Vaporizer and vapor phase growth apparatus
US11/593,110 US7672575B2 (en) 2005-11-07 2006-11-06 Evaporator featuring annular ridge member provided on side wall surface of evaporating chamber
JP2007129152A JP2007129152A (en) 2007-05-24
JP4828918B2 true JP4828918B2 (en) 2011-11-30
ID=38151534
JP2005322412A Expired - Fee Related JP4828918B2 (en) 2005-11-07 2005-11-07 Vaporizer and vapor phase growth apparatus
US (1) US7672575B2 (en)
JP (1) JP4828918B2 (en)
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JP2006135053A (en) * 2004-11-05 2006-05-25 Tokyo Electron Ltd Evaporizer and depositing device
2005-11-07 JP JP2005322412A patent/JP4828918B2/en not_active Expired - Fee Related
2006-11-06 US US11/593,110 patent/US7672575B2/en active Active
US20070151518A1 (en) 2007-07-05
US7672575B2 (en) 2010-03-02
JP2007129152A (en) 2007-05-24
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