JP2009132548A - Growth apparatus and growth method of group iii nitride crystal - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing apparatus and a manufacturing method of a group III nitride crystal which prevents mingling of residual gases in dead spaces of piping and an atmospheric gas in a reactor vessel into the reactor vessel and prevents degradation of physical properties of the group III nitride crystal. <P>SOLUTION: The manufacturing apparatus of the group III nitride crystal comprises first piping 10 to connect the reactor vessel 1 and a nitrogen raw material gas supply apparatus 7, second piping 20 to connect the first piping 10 and a first evacuating apparatus 8, and a first airtight partition 11d formed halfway in the first piping 10. The reactor vessel 1 is made airtight by the first airtight partition 11d. When the interior of the first and the second piping 10, 20 is evacuated, or when a nitrogen raw material gas 9 is supplied into the reactor vessel 1, the airtightness of the first airtight partition 11d of the first piping 10 is broken by a pressure difference between the reactor vessel 1 side and the nitrogen raw material gas supply apparatus 7 side. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a growth apparatus and a growth method suitable for growing a group III nitride crystal.

  A flux method has been proposed as a method for growing a large group III nitride crystal having high crystallinity suitably used for substrates of various semiconductor devices such as LED (light emitting diode) and LD (laser diode) by a liquid phase method. (For example, refer to Japanese Patent Application Laid-Open No. 2001-064097 (Patent Document 1)).

  However, since such a flux method uses an alkali metal or alkaline earth metal melt as the flux, there is a problem that the flux is easily oxidized by oxygen or moisture and the physical properties of the group III nitride crystal to be grown are lowered.

  For this reason, in the growth of Group III nitride crystals by the flux method, it is necessary to minimize the mixing of oxygen and moisture into the reaction vessel.

For this reason, it has been proposed that the step of introducing the alkali metal element-containing material as a flux into the reaction vessel is performed in an inert gas (N ₂ gas, Ar gas) atmosphere having a moisture concentration of 1.0 ppm or less (for example, JP, 2005-298269, A (patent documents 2)). It has also been proposed to connect a check valve to the reaction vessel to control the crystal growth atmosphere gas in the reaction vessel (see, for example, JP-A-2006-160567 (Patent Document 3)).
JP 2001-064097 A JP 2005-298269 A JP 2006-160567 A

  However, the alkali metal element and the alkaline earth disposed in the reaction vessel can be obtained by any of the methods described in JP-A-2005-298269 (Patent Document 2) and JP-A-2006-160567 (Patent Document 3). A gas remaining in a dead space of a pipe for supplying a nitrogen raw material gas to a melt of a raw material containing at least one kind of metal element and a group III metal element is mixed in the reaction vessel; and It was not possible to prevent the atmospheric gas in the pressure vessel from being mixed into the reaction vessel. For this reason, it has been difficult to prevent deterioration of the physical properties of the group III nitride crystal due to the mixing of oxygen or moisture in these gases. Of course, it is not desirable that air containing oxygen or moisture is mixed into the reaction vessel. In addition, the heat insulating material in the pressure vessel is exposed to the atmosphere before and after crystal growth to absorb moisture, and is heated during crystal growth to release the absorbed moisture. For this reason, it is extremely important to obtain a high-purity nitride crystal so that the atmospheric gas outside the reaction vessel is not mixed into the reaction vessel from the start to the end in the pressure vessel. .

  Moreover, it is difficult to use a quick connector, a check valve or the like inside the pressure vessel and outside the reaction vessel. For example, the temperature inside the pressure vessel and outside the reaction vessel in the flux method becomes a high temperature of about 300 ° C. to 600 ° C. due to the arrangement of the heat insulating material and the piping. That is, in order to grow as large a crystal as possible, the gap between the reaction vessel, the heat insulating material and the pressure vessel is limited in order to make the volume of the reaction vessel as large as possible within the limited volume of the pressure vessel. It is difficult to make the temperature outside the reaction vessel 300 ° C. or lower, and it is further difficult to make it 204 ° C. or lower. For quick connectors, check valves, etc., the O-ring is used for the seal portion, so the usable temperature is up to about 204 ° C. For this reason, when a quick connector or check valve is used, the O-ring of the quick connector or check valve is deteriorated by exposure to an ambient temperature of 300 to 600 ° C. during crystal growth. Moisture-containing atmospheric gas is mixed into the reaction vessel, the dew point in the reaction vessel rises, the optical absorption coefficient of the grown group III nitride crystal increases, and crystal defects such as cracks increase. .

  The lift type check valve can be used up to about 482 ° C., but since the stainless steel is used for the seal portion, the airtightness is insufficient. For this reason, during crystal growth, atmospheric gas containing oxygen or moisture in the pressure vessel is mixed into the reaction vessel, the dew point in the reaction vessel rises, and the grown group III nitride crystal optically grows. Absorption coefficient increases and crystal defects such as cracks increase.

  In order to solve the above problems, the present invention is such that residual gas in the dead space of piping and atmospheric gas outside the reaction vessel are mixed in the reaction vessel in the pressure vessel without using a quick connector, a check valve, etc. It is an object of the present invention to provide a group III nitride crystal manufacturing apparatus and method capable of preventing deterioration of physical properties of a group III nitride crystal due to oxygen or moisture mixed in the residual gas and atmospheric gas. To do.

  The present invention includes a reaction vessel, a pressure vessel that accommodates the reaction vessel, a nitrogen source gas supply device, a first vacuum exhaust device, and a reaction vessel and a nitrogen source gas supply device that penetrate the wall of the pressure vessel. Between the 1st piping to connect, the 1st airtight partition formed in the middle of the inside of the pressure vessel of the 1st piping, and the nitrogen source gas supply device of the 1st piping, and the 1st airtight partition And a second pipe connecting the first vacuum evacuation device and the reaction vessel is hermetically sealed by the first hermetic partition, and the inside of the first and second pipes is evacuated. Alternatively, when supplying the nitrogen source gas into the reaction vessel, the first hermetic partition is a group III nitride crystal growth device that is removed by a pressure difference between the reaction vessel side and the nitrogen source gas supply device side.

  In the group III nitride crystal growth apparatus according to the present invention, the first hermetic partition may be a thin film, and a filter may be provided on at least one side of the first hermetic partition in the first pipe. Here, the first hermetic partition has a first locking portion between the first locking portion of the first pipe portion of the first pipe and the second locking portion of the second pipe portion of the first pipe. It can be fixed by a first joint member having a third locking portion corresponding to the portion and a fourth locking portion corresponding to the second locking portion. Also, the first hermetic partition can be a liquid.

  Further, in the group III nitride crystal growth apparatus according to the present invention, a third pipe extending from the reaction vessel through the wall of the pressure vessel to the atmosphere, and an inner side of the pressure vessel of the third pipe A second hermetic partition formed in the middle of the reactor, the reaction vessel being hermetically sealed by the second hermetic partition, and when supplying the nitrogen source gas to the reaction vessel, the second hermetic partition The airtightness of the reactor is broken by the pressure difference between the reaction vessel side and the atmosphere side.

  Further, in the group III nitride crystal growth apparatus according to the present invention, the second vacuum evacuation apparatus, a valve formed in the middle of the pressure vessel of the third pipe, and the third pipe of the third pipe And a fourth pipe connecting the second vacuum evacuation device and a pipe portion between the second airtight partition and the valve, and when the inside of the third and fourth pipes is evacuated or in the reaction vessel When supplying the nitrogen source gas, the airtightness of the second airtight partition is broken by the pressure difference between the reaction vessel side and the atmosphere side.

  Further, a valve formed in the middle of the pressure vessel of the third pipe, a pipe portion between the second hermetic partition of the third pipe and the valve, and a pipe in the middle of the second pipe A fourth pipe connecting the first and second parts, and when evacuating the inside of the first, second, third and fourth pipes or supplying the nitrogen source gas to the reaction vessel, The airtightness of the airtight partition is broken by the pressure difference between the reaction vessel side and the atmosphere side.

  In the group III nitride crystal manufacturing apparatus according to the present invention, the second hermetic partition can be a thin film, and a filter is provided on at least one side of the second hermetic partition in the third pipe. it can. Here, the second airtight partition has a fifth locking portion between the fifth locking portion of the third pipe portion of the third pipe and the sixth locking portion of the fourth pipe portion of the third pipe. It can be fixed by a second joint member having a seventh locking portion corresponding to the portion and an eighth locking portion corresponding to the sixth locking portion. Also, the second hermetic partition can be a liquid.

  Further, the present invention is a method for growing a group III nitride crystal using the above growth apparatus, wherein at least one element selected from the group consisting of an alkali metal element and an alkaline earth metal element and III A step of arranging a raw material containing a group metal element, a step of evacuating the inside of the first and second pipes, and a step of supplying a nitrogen raw material gas into the reaction vessel, and a step of evacuating or nitrogen This is a method for growing a group III nitride crystal in which the airtightness of the first hermetic partition is broken by the pressure difference between the reaction vessel side and the nitrogen source gas supply device side in the step of supplying the source gas.

  Further, the present invention is a method for growing a group III nitride crystal using the above growth apparatus, wherein at least one element selected from the group consisting of an alkali metal element and an alkaline earth metal element and III A step of arranging a raw material containing a group element, a step of evacuating the inside of the first and second pipes, and a step of supplying a nitrogen raw material gas into the reaction vessel, and evacuating or nitrogen In the step of supplying the raw material gas, the airtightness of the first hermetic partition is broken by the pressure difference between the reaction vessel side and the nitrogen raw material gas supply device side, and in the step of supplying the nitrogen raw material gas, the airtightness of the second hermetic partition Is a method for growing a group III nitride crystal that is broken by a pressure difference between the reaction vessel side and the atmosphere side.

  Further, the present invention is a method for growing a group III nitride crystal using the above growth apparatus, wherein at least one element selected from the group consisting of an alkali metal element and an alkaline earth metal element and III A raw material containing a group element, a first evacuation step for evacuating the interior of the first and second pipes, and a second evacuation for evacuating the interior of the third and fourth pipes A vacuum evacuation step of at least one of the steps, and a step of supplying a nitrogen source gas into the reaction vessel, wherein the first hermetic partition has airtightness in the first evacuation step or the step of supplying the nitrogen source gas. The airtightness is broken by the pressure difference between the reaction vessel side and the nitrogen source gas supply device side, and the airtightness of the second hermetic partition is the reaction vessel side in the second evacuation step or the nitrogen source gas supply step. It is a method of growing III-nitride crystal to be broken by the pressure difference between the atmosphere side.

  Further, the present invention is a method for growing a group III nitride crystal using the above growth apparatus, wherein at least one element selected from the group consisting of an alkali metal element and an alkaline earth metal element and III A step of disposing a raw material containing a group element, a step of evacuating the inside of the first, second, third and fourth pipes, and a step of supplying a nitrogen raw material gas into the reaction vessel. In the step of exhausting or supplying the nitrogen source gas, the airtightness of the first hermetic partition is broken by the pressure difference between the reaction vessel side and the nitrogen source gas supply side, and the step of evacuating or the nitrogen source gas is reduced. A method for growing a group III nitride crystal in which the airtightness of the second airtight partition is broken by a pressure difference between the reaction vessel side and the atmosphere side in the supplying step.

  According to the present invention, it is possible to prevent the residual gas in the dead space of the piping from being mixed into the reaction vessel, and to prevent the deterioration of the physical properties of the group III nitride crystal due to the mixing of oxygen or moisture in the residual gas. An apparatus and a method for producing a group III nitride crystal can be provided.

(Embodiment 1)
Referring to FIG. 1, one embodiment of a group III nitride crystal production apparatus according to the present invention includes a reaction vessel 1, a pressure vessel 5 containing the reaction vessel 1, a nitrogen source gas supply device 7, 1 evacuation device 8, a first pipe 10 that passes through the wall of the pressure vessel 5 and connects the reaction vessel 1 and the nitrogen source gas supply device 7, and a first pipe 10 on the inner side of the pressure vessel 5. A first airtight partition 11d formed in the middle, and a tube portion 10b (hereinafter also referred to as a second tube portion) between the nitrogen source gas supply device 7 of the first pipe 10 and the first airtight partition 11d. ) And the second piping 20 connecting the first vacuum exhaust device 8, the reaction vessel 1 is hermetically sealed by the first hermetic partition 11 d, and the interior of the first and second piping 10, 20 When evacuating or supplying the nitrogen source gas 9 to the reaction vessel 1, Airtightness of the first airtight partition 11d 10 is broken by the pressure difference between the reaction vessel 1 side and the nitrogen source gas supply unit 7 side (i.e. the first evacuator 8 side).

  Here, with reference to FIG. 1, FIG. 5 (a) or FIG. 8, the 1st airtight partition 11d is provided so that the 1st piping 10 may be obstruct | occluded in the place. The first hermetic partition 11d keeps the reaction vessel 1 airtight before the growth of the group III nitride crystal. When the air tightness of the first airtight partition 11d is broken during the vacuum exhaust, the residual gas in the first and second pipes 10 and 20 and the reaction vessel 1 and the oxygen or moisture contained therein are efficiently removed by the vacuum exhaust. Removed. Further, when the airtightness of the first airtight partition 11d is broken not during the vacuum exhaustion but during the subsequent supply of the nitrogen raw material, the residual gas in the first and second pipes 10 and 20 and the The oxygen and moisture contained in it are removed very efficiently. Even if the airtightness of the first airtight partition 11d is broken, the atmospheric gas in the pressure vessel 5 containing oxygen or moisture is high because the airtightness of the first and second pipes 10, 20 and the reaction vessel 1 is high. Can be prevented from being mixed into the reaction vessel 1. For this reason, the physical property fall by mixing of the oxygen or the water | moisture content of the group III nitride crystal grown in the reaction container 1 can be prevented. Here, due to the mixing of oxygen or moisture in the residual gas, the group III nitride crystal has an increased optical absorption coefficient and crystal defects such as cracks.

  Referring to FIG. 1, the group III nitride crystal manufacturing apparatus of this embodiment includes a reaction vessel 1 for growing a group III nitride crystal, a pressure vessel 5 for housing the reaction vessel 1, and a later-described embodiment. The first and second pipes 10 and 20 and the first vacuum evacuation device 8 for evacuating the interior of the reaction vessel 1 and the nitrogen gas for supplying the nitrogen source gas 9 into the reaction vessel 1. And a supply device 7. Inside the reaction vessel 1, a crucible 2 for placing a flux of alkali metal elements, alkaline earth metal elements and the like and a group III metal element raw material is disposed. A heater 3 for heating the inside of the reaction vessel 1 is disposed around the reaction vessel 1, and a heat insulating material 4 is formed so as to surround the reaction vessel 1 and the heater 3. In this way, the reaction vessel 1 in which the heater 3 and the heat insulating material 4 are arranged is accommodated in the pressure vessel 5.

  Here, the material of the reaction vessel 1 is not particularly limited, but stainless steel and the like are preferable from the viewpoint of high heat resistance and corrosion resistance. Further, the material of the crucible 2 is not particularly limited, but aluminum oxide and the like are preferably used from the viewpoint of not contaminating the nitride crystal and having high heat resistance and corrosion resistance. The material of the heater 3 is not particularly limited, but preferred is siliconite (silicon carbide heating element), Kanthal, etc. from the viewpoint of low gas generation and high durability. The material of the heat insulating material 4 is not particularly limited, but carbon, ceramics, glass wool, and the like are preferable from the viewpoint of high heat insulating properties and heat resistance. Further, the material of the pressure vessel 5 is not particularly limited, but stainless steel is preferably used from the viewpoint of high durability.

  In addition, a first pipe 10 that connects the reaction vessel 1 and the nitrogen source gas supply device 7 is provided, and a first airtight partition 11 d is formed in the middle of the pressure vessel 5 of the first pipe 10. ing. That is, the first pipe 10 is connected between the reaction vessel 1 and the first airtight partition 11d between the tube portion 10a (first tube portion) and the first airtight partition 11d and the nitrogen source gas supply device 7. Tube portion 10b (second tube portion). A valve 7 v is provided at the outlet of the nitrogen source gas supply device 7.

  In addition, the second pipe 20 connecting the pipe portion 10b (second pipe section) between the nitrogen source gas supply device 7 of the first pipe 10 and the first hermetic partition 11d and the first vacuum exhaust device 8. Is provided. A valve 8 v is provided at the inlet portion of the first vacuum exhaust device 8. Here, the material of the first and second pipes 10 and 20 is not particularly limited, but stainless steel and the like are preferable from the viewpoint of high heat resistance and durability.

  Furthermore, the group III nitride crystal manufacturing apparatus of the present embodiment includes a first joint 13 provided in the middle of the first pipe 10. In the first pipe 10, the first joint 13 is between the joint 10j between the first pipe 10 and the second pipe 20 and the first airtight partition 11d, and is a pressure vessel. 5 is provided on the inner side. That is, the pipe part 10b (second pipe part) between the first airtight partition 11d and the nitrogen source gas supply device 7 is the pipe part 10ba (second pipe part) between the first airtight partition 11d and the first joint 13. A fifth pipe section) and a pipe section 10bb (sixth pipe section) bb between the first joint 13 and the nitrogen source gas supply device 7.

  Accordingly, the first pipe 10 includes a pipe portion 10a (first pipe portion) between the reaction vessel 1 and the first airtight partition 11d, and a space between the first airtight partition 11d and the first joint 13. A pipe part 10ba (fifth pipe part) and a pipe part 10bb (sixth pipe part) between the first joint 13 and the nitrogen source gas supply device 7 are provided.

  For this reason, the first pipe 10 includes the pipe parts 10a (first pipe part) and 10ba (fifth pipe part) fixed to the reaction vessel 1, the pressure vessel 5 and the first joint 13 by removing the first joint 13. It is divided into a tube portion 10bb (sixth tube portion) fixed to the nitrogen source gas supply device 7. That is, the reaction vessel 1 can be taken in and out from the pressure vessel 5.

  Referring to FIG. 5, before the growth of the group III nitride crystal, the reaction vessel 1 is kept airtight by the first airtight partition 11d (FIG. 5 (a)). When the group III nitride crystal is grown, first, the insides of the first and second pipes 10 and 20 are exhausted by the first vacuum exhaust device 8. At this time, if the airtightness of the first airtight partition 11d is designed to be broken at a pressure lower than 1 atm (100 kPa), the airtightness of the first airtight partition 11d is It is broken by the pressure difference between the reaction vessel 1 side and the first vacuum evacuation device 8 side (namely, the nitrogen source gas supply device 7 side) (FIG. 5B), and the inside of the reaction vessel 1 is also evacuated. In addition, when the airtightness of the first airtight partition 11d is designed to be broken at a pressure higher than 1 atm (100 kPa), the airtightness of the first airtight partition 11d is In the subsequent supply of the nitrogen source gas 9 to the reaction vessel 1, it is broken by the pressure difference between the reaction vessel 1 side and the nitrogen source gas supply device 7 side (that is, the first vacuum exhaust device 8 side). (FIG. 5B).

  Referring to FIGS. 1 and 5, the first hermetic partition 11d is not particularly limited, but is preferably a thin film from the viewpoint of easily breaking its hermeticity. The thin film is not particularly limited, but is preferably a metal film from the viewpoint of heat resistance and chemical stability. Examples of the metal film include an aluminum film and a stainless film.

  When the first hermetic partition 11d is a thin film, referring to FIGS. 1 and 6, from the viewpoint of preventing the inside of the first evacuation apparatus 8 or the reaction vessel 1 due to the scattering of the broken thin film, It is preferable that filters 12a and 12b are provided on at least one side of the first hermetic partition 11d. Here, the material of the filters 12a and 12b is not particularly limited, but stainless steel and the like are preferable from the viewpoint of high heat resistance and corrosion resistance.

  Referring to FIG. 7, when the first hermetic partition 11d is a thin film, the first hermetic partition 11d is a first locking portion of the tube portion 10a (first tube portion) of the first pipe 10. Between F1 and the 2nd latching | locking part F2 of the pipe part 10b (2nd pipe part) of the 1st piping 10, the 3rd latching | locking part F3 and 2nd latching | locking part corresponding to the 1st latching | locking part F1. It is preferable to be fixed by a first joint member 11c having a fourth locking portion F4 corresponding to F2. In this way, the first hermetic partition 11d is fixed to the first pipe 10 with good airtightness. Thus, the joint including the first hermetic partition 11d is referred to as a first hermetic partition-attached joint 11. The first airtight partition 11d is preferably fixed between the first locking portion F1 and the second locking portion F2 together with the gasket 11s from the viewpoint of improving the airtightness. Here, the material of the gasket 11s is not particularly limited, but stainless steel and the like are preferable from the viewpoint of high heat resistance and corrosion resistance.

  1 and 8, the first hermetic partition 11d is not particularly limited, but is preferably a liquid from the viewpoint of easily breaking its hermeticity. The method for using the liquid as the first hermetic partition is not particularly limited. For example, a part of the first pipe 10 is bent into a ring shape (FIG. 8A), or one of the first pipes 10 is used. The liquid can be used as a first hermetic partition by bending the part into a U-shape (FIG. 8B) and disposing the liquid in the bent part. Here, when the first hermetic partition 11d is a liquid, the liquid serving as the first hermetic partition 11d may be the reaction container 1 side or the nitrogen raw material due to a pressure difference between the reaction container 1 side and the nitrogen raw material gas supply device 7 side. By removing to the gas supply device 7 side (that is, the first vacuum exhaust device 8 side), the airtightness is broken.

  The liquid is not particularly limited, but is preferably a Group III metal element melt from the viewpoint of little influence when mixed inside the reaction vessel 1, and mixed into the first vacuum exhaust device 8. From the viewpoint of reducing the influence of the evacuation, it is preferable to use an oil for a vacuum exhaust device. In addition, as the first hermetic partition 11d, two bent portions are prepared in the first pipe, and the group III metal element melt is applied to the bent portion close to the reaction vessel, and the bent portion closer to the vacuum exhaust device is vacuumed. It is also preferable to arrange oil for the exhaust device (not shown).

  Furthermore, in order to prevent the liquid from entering the reaction vessel 1 or the inside of the first vacuum exhaust device 8, at least one side of the liquid first hermetic partition 11d, for example, the first vacuum exhaust device 8 is used. It is also preferable to provide a trap on the side (namely, the nitrogen source gas supply device 7 side) (not shown).

  In addition, referring to FIG. 1, in order to enable the reaction vessel 1 to be taken in and out from the pressure vessel 5, a joint 10 j between the first pipe 10 and the second pipe 20 in the first pipe 10. The first joint 13 is provided on the inner side of the pressure vessel 5 between the first airtight partition 11d and the inner side of the pressure vessel 5.

  Here, with reference to FIG. 10, in the first joint 13, in the pipe portion 10 b (second pipe portion) of the first pipe, the ninth locking portion of the pipe portion 10 ba (fifth pipe portion). Between F9 and the tenth locking portion F10 of the tube portion 10bb (sixth tube portion), an eleventh locking portion F11 corresponding to the ninth locking portion F9 and a twelfth corresponding to the tenth locking portion F10. The tip of the third tube portion 10ba and the tip of the fourth tube portion 10bb are joined by the third joint member 13c having the locking portion F12 with the gasket 13s interposed therebetween.

(Embodiment 2)
One embodiment of a method for growing a group III nitride crystal according to the present invention is a method for growing a group III nitride crystal using the growth apparatus of embodiment 1 with reference to FIG. Placing the raw material 6 containing at least one element selected from the group consisting of an alkali metal element and an alkaline earth metal element and a group III metal element, and evacuating the interior of the first and second pipes 10 and 20; A step of evacuating and a step of supplying the nitrogen source gas 9 into the reaction vessel 1, and in the step of evacuating or supplying the nitrogen source gas 9, the airtightness of the first hermetic partition 11 d is the reaction vessel 1 side. And the nitrogen source gas supply device 7 side (that is, the first vacuum exhaust device 8 side).

  Before the growth of the group III nitride crystal, the first hermetic partition 11d keeps the reaction vessel 1 airtight before the growth of the group III nitride crystal. When the airtightness of the first airtight partition 11d is broken in the evacuation process, the gas remaining in the first and second pipes 10, 20 and the reaction vessel 1 is efficiently removed by the evacuation process. The Further, when the airtightness of the first airtight partition 11d is broken in the step of supplying the nitrogen source gas after the step of evacuating, the first and second pipes 10 and 20 remain in the step of evacuating. Gas is removed very efficiently. Even if the airtightness of the first airtight partition 11d is broken, the atmospheric gas in the pressure vessel 5 containing oxygen or moisture is high because the airtightness of the first and second pipes 10, 20 and the reaction vessel 1 is high. Can be prevented from being mixed into the reaction vessel 1. For this reason, the physical property fall by mixing of the oxygen or the water | moisture content of the group III nitride crystal grown in the reaction container 1 can be prevented.

  Referring to FIG. 1, the method for growing a group III nitride crystal of the present embodiment includes the following steps. First, referring to FIG. 9A, an alkali metal element and an alkaline earth metal element are placed in the crucible 2 in the reaction vessel 1 to which the pipe part 10a (first pipe part) of the first pipe is connected. A raw material 6 containing at least one element selected from the group consisting of and a group III metal element is disposed (arrangement step of the raw material in the reaction vessel). It is preferable to perform the raw material arrangement step in the reaction vessel in a nitrogen gas or argon gas atmosphere of 1 atm (100 kPa) dried in the drying vessel in order to prevent oxygen or moisture from being mixed into the raw material 6. Moreover, it is preferable that the water concentration in a dry container is 1.0 ppm or less, and it is more preferable that it is 0.54 ppm or less. Here, the other end of the tube portion 10a (first tube portion) whose one end is connected to the reaction vessel 1 is connected to one end of the joint 11 having the first hermetic partition provided with the first hermetic partition 11d. The other end of the airtight partition joint 11 is connected to one end of the pipe portion 10ba (fifth pipe portion) of the first pipe.

  Next, the reaction vessel 1 in which the raw material 6 is arranged is accommodated in a predetermined position in a pressure vessel 5 provided with a heater 3 and a heat insulating material 4 (accommodating step of the reaction vessel into the pressure vessel). At this time, the reaction vessel 1 is hermetically sealed by the first hermetic partition 11d.

  Next, referring to FIG. 1, the other end of the pipe part 10 ba (fifth pipe part) whose one end is connected to the first airtight partition joint 11 is connected to the first pipe by the first joint 13. This is connected to one end of the tube portion 10bb (sixth tube portion). Here, the other end of the pipe part 10bb (sixth pipe part) is connected to the nitrogen source gas supply device 7 via a valve 7v. In addition, one end of the second pipe 20 is connected to the middle of the pipe part 10bb (sixth pipe part) (joint part 10j between the first pipe 10 and the second pipe 20), and the other of the second pipe 20 The end is connected to the first vacuum exhaust device 8 through a valve 8v. That is, by connecting the pipe part 10ba (fifth pipe part) and the pipe part 10bb (sixth pipe part) by the first joint 13, the reaction vessel 1 and the nitrogen source gas supply device 7 are connected by the first pipe 10. The reaction vessel 1 and the first vacuum exhaust device 8 are connected by the second pipe 20.

  Next, the inside of the first and second pipes 10 and 20 is evacuated by the first evacuation apparatus 8 (evacuation process). At this time, when the airtightness of the first airtight partition 11d is designed to be broken by a pressure of 1 atm (100 kPa) or less, the airtightness of the first airtight partition 11d is determined in the reaction vessel in the vacuum exhaust process. It is broken by the pressure difference between the first side and the first evacuation device 8 side (that is, the nitrogen source gas supply device 7 side). In such a case, the residual gas in the first and second pipes 10 and 20 and the reaction vessel 1 and the oxygen or moisture contained therein can be efficiently removed by the evacuation process.

  In addition, when the airtightness of the first airtight partition 11d is designed to be broken at a pressure higher than 1 atm (100 kPa), the airtightness of the first airtight partition 11d is Is not broken, and during the subsequent supply of the nitrogen source gas 9 to the reaction vessel 1, due to the pressure difference between the reaction vessel 1 side and the nitrogen source gas supply device 7 side (that is, the first vacuum exhaust device 8 side) Torn. In such a case, the gas remaining in the first and second pipes 10 and 20 and the oxygen or moisture contained therein are removed very efficiently by the evacuation process. For this reason, mixing of oxygen or moisture into the reaction vessel 1 is prevented.

  Here, the degree of vacuum of the first and second pipes 10 and 20 and the reaction vessel 1 when evacuated is not particularly limited, but the better the degree of vacuum, the more the residual gas and oxygen or moisture contained therein are removed. Is done. From this viewpoint, the degree of vacuum is preferably 1 kPa or less, and more preferably 1 Pa or less.

  Next, the nitrogen source gas 9 is supplied from the nitrogen source gas supply device 7 into the reaction vessel 1 through the first pipe 10 (nitrogen source gas supply step). The nitrogen source gas 9 is not particularly limited, but nitrogen gas is preferable from the viewpoint of growing a high-purity group III nitride crystal. At least selected from the group consisting of alkali metal elements and alkaline earth metal elements by heating the raw material 6 disposed in the crucible 2 of the reaction vessel 1 by the heater 3 together with the supply of the nitrogen raw material gas 9 to the reaction vessel 1. A melt containing one kind of element and a group III metal element is used. The group III nitride crystal grows by dissolving the nitrogen source gas 9 in the raw material 6 which is the melt. Such a group III nitride crystal has a high physical property because it is grown in the reaction vessel 1 from which oxygen or moisture is efficiently removed and mixing of oxygen or moisture is prevented.

(Embodiment 3)
Another embodiment of the group III nitride crystal production apparatus according to the present invention is described in the production apparatus of the first embodiment with reference to FIG. The reaction vessel 1 further includes a third pipe 30 drawn out and a second airtight partition 31d formed in the middle of the pressure vessel 5 of the third pipe 30, and the reaction vessel 1 has a second airtight partition. When the nitrogen raw material gas 9 is supplied to the reaction vessel 1, the airtightness of the second airtight partition 31 d is the pressure between the reaction vessel 1 side and the atmospheric side (opposite side of the reaction vessel 1). Break by difference.

  Here, as in the case of the manufacturing apparatus of the first embodiment, when the airtightness of the first hermetic partition 11d is broken during the evacuation, the manufacturing apparatus of the present embodiment performs the first and second operations by evacuation. Residual gases in the pipes 10 and 20 and the reaction vessel 1 and oxygen or moisture contained therein are efficiently removed. Further, when the airtightness of the first airtight partition 11d is broken not during the vacuum exhaustion but during the subsequent supply of the nitrogen raw material, the residual gas in the first and second pipes 10 and 20 and the The oxygen and moisture contained in it are removed very efficiently. Even if the airtightness of the first airtight partition 11d is broken, since the airtightness of the first, second and third pipes and the reaction vessel is high, the atmospheric gas in the pressure vessel 5 containing oxygen or moisture is Mixing into the reaction vessel 1 can be prevented. For this reason, the physical property fall by mixing of the oxygen or the water | moisture content of the group III nitride crystal grown in the reaction container 1 can be prevented.

  Furthermore, in addition to the manufacturing apparatus of the first embodiment, the manufacturing apparatus of the present embodiment includes a third pipe 30 that extends from the reaction vessel 1 through the wall of the pressure vessel 5 to the atmosphere, and a third pipe 30. Since the second hermetic partition 31d formed in the middle of the pressure vessel 5 of the pipe 30 is provided, new nitrogen is introduced into the reaction vessel 1 through the first pipe 1 when the group III nitride crystal is grown. The raw material gas 9 can be introduced, and the residual gas inside the reaction vessel 1 can be discharged from the third pipe 30. For this reason, while maintaining the predetermined pressure of the nitrogen source gas 9 in the reaction vessel 1, the unreacted gas inside the reaction vessel 1 and the residual gas after the reaction and impurities contained therein are flowed out, The atmospheric gas in the pressure vessel 5 containing oxygen or moisture can be prevented from being mixed into the reaction vessel 1, and the physical properties of the group III nitride crystal to be grown can be further prevented from deteriorating.

  The group III nitride crystal manufacturing apparatus of the present embodiment is the same as the manufacturing apparatus of the first embodiment with respect to the first pipe 10 in which the first hermetic partition 11d is formed in the middle of the pressure vessel 5. Therefore, what has been described in the manufacturing apparatus of the first embodiment is also applicable to the manufacturing apparatus of the present embodiment as it is.

  Therefore, in the group III nitride crystal production apparatus of the present embodiment, the first hermetic partition 11d is preferably a thin film (see FIGS. 2 and 5), as in the first embodiment. 10, filters 12a and 12b are preferably provided on at least one side of the first hermetic partition 11d (see FIGS. 2 and 6). The first hermetic partition 11d includes the first locking part F1 of the pipe part 10a (first pipe part) of the first pipe 10 and the first pipe part 10b (second pipe part) of the first pipe 10. The first joint member 11c having a third locking portion F3 corresponding to the first locking portion F1 and a fourth locking portion F4 corresponding to the second locking portion F2 between the two locking portions F2. It is preferably fixed (see FIG. 7). Moreover, it is preferable that the 1st airtight partition 11d is a liquid (refer FIG. 8).

  The group III nitride crystal manufacturing apparatus of the present embodiment has the following configuration added to the manufacturing apparatus of the first embodiment with reference to FIG. The manufacturing apparatus of this embodiment is provided with a third pipe 30 that extends from the reaction vessel 1 through the wall of the pressure vessel 5 and is drawn into the atmosphere. A second airtight partition 31 d is formed in the middle of the pressure vessel 5 of the third pipe 30. Here, the 2nd airtight partition 31d is provided so that the 3rd piping 30 may be obstruct | occluded in the place. The reaction vessel 1 is hermetically sealed by a first hermetic partition 11 d of the first pipe 10 and a second hermetic partition 31 d of the third pipe 30. Here, the material of the third pipe 30 is not particularly limited, but is preferably the same as that of the first and second pipes 10 and 20.

  When the inside of the first and second pipes 10 and 20 and the reaction vessel 1 is evacuated, the airtightness of the second airtight partition 31d needs to be maintained. Therefore, the second hermetic partition 31d is designed to have a pressure resistance higher than 1 atm (100 kPa). Further, when the nitrogen source gas 9 is supplied to the reaction vessel 1 by the nitrogen source gas supply device 7, the second hermetic partition 31 d is removed, and the unreacted gas and the like can be discharged from the reaction vessel 1. There is a need. For this reason, the second hermetic partition 31d is designed such that its hermeticity is broken at a pressure lower than the nitrogen source gas pressure (usually about 2 to 7.5 MPa) during crystal growth. For example, the second hermetic partition 31d is designed so that the pressure resistance is 0.5 MPa.

  In the group III nitride crystal manufacturing apparatus of the present embodiment, the second hermetic partition 31d is not particularly limited, but from the viewpoint of easily breaking its hermeticity, like the first hermetic partition 11d, A thin film is preferred. Although there is no restriction | limiting in particular in a thin film, From a viewpoint of heat resistance and chemical stability, it is preferable that it is a metal film similarly to the 1st airtight partition 11d. Examples of the metal film include an aluminum film and a stainless film.

  However, secondly, since the airtightness of the airtight partition 31d is broken after the airtightness of the first airtight partition 11d is broken, the second airtight partition 31d is higher than the first airtight partition 11d. Need to withstand pressure. For this reason, the second hermetic partition 31d secures high pressure resistance by using a material having high mechanical strength or by increasing the film thickness as compared with the first hermetic partition 11d.

  Further, when the second hermetic partition 31d is a thin film, as in the case of the first hermetic partition 11d, referring to FIG. 2, the mixing of the broken thin film into the reaction vessel 1 due to scattering is prevented. From the viewpoint, it is preferable that filters 32a and 32b are provided on at least one side of the second hermetic partition 31d. Here, the material of the filters 32a and 32b is not particularly limited, but stainless steel and the like are preferable from the viewpoint of high heat resistance and corrosion resistance.

  When the second hermetic partition 31d is a thin film, the second hermetic partition 31d is the fifth locking portion of the third pipe portion of the third pipe 30 as in the case of the first hermetic partition 11d. And a seventh locking portion corresponding to the fifth locking portion and an eighth locking portion corresponding to the sixth locking portion between the second locking portion and the sixth locking portion of the fourth pipe portion of the third pipe 30. It is being fixed by the 2nd joint member which has.

  The second airtight partition joint 31 provided with the second airtight partition 31d has the same structure as the first airtight partition joint 11 provided with the first airtight partition 11d shown in FIG. The partition 31d, the third pipe portion of the third pipe, the fourth pipe portion of the third pipe, the fifth locking portion, the sixth locking portion, the seventh locking portion, and the eighth locking portion are respectively illustrated. 7d, the first pipe section 10a (first pipe section), the first pipe section 10b (second pipe section), the first locking section F1, the second engagement section. It corresponds to the stop portion F2, the third locking portion F3, and the fourth locking portion F4.

  With this structure, the second airtight partition 31d is fixed to the third pipe 30 with good airtightness. It is preferable that the second airtight partition 31d is fixed between the fifth locking portion and the sixth locking portion together with the gasket from the viewpoint of improving the airtightness. Here, the material of the gasket is not particularly limited, but stainless steel and the like are preferable from the viewpoint of high heat resistance and corrosion resistance.

  The second hermetic partition 31d is not particularly limited, but is preferably a liquid from the viewpoint of easily breaking its hermeticity, like the first hermetic partition 11d. The method of using the liquid as the second hermetic partition 31d is not particularly limited, and, for example, a part of the third pipe 30 is bent into a ring shape or the third pipe as in the first hermetic partition. The liquid can be used as the second hermetic partition by bending a part of the 30 into a U shape and disposing the liquid in the bent portion. Here, when the second hermetic partition 31d is a liquid, the liquid serving as the second hermetic partition 31d is changed to the reaction container 1 side or the pressure difference between the reaction container 1 side and the atmosphere side (the side opposite to the reaction container). By removing to the atmosphere side, its airtightness is broken.

  The liquid is not particularly limited, but is preferably a Group III metal element melt from the viewpoint of little influence when mixed in the reaction vessel 1. Alternatively, it is possible to use pump oil that does not interfere with mixing in the vacuum exhaust device. Furthermore, it is also preferable to provide a trap on at least one side of the liquid second hermetic partition 31d in order to prevent the liquid from mixing into the reaction vessel.

  Further, referring to FIG. 2, in order to enable the reaction vessel 1 to be taken in and out from the pressure vessel 5, a joint 10 j between the first pipe 10 and the second pipe 20 in the first pipe 10. And the first airtight partition 11d, and the first joint 13 is provided on the inner side of the pressure vessel 5. In the third pipe 30, a second joint 33 is provided on the inner side of the pressure vessel 5.

  Here, the first joint 13 is the same as that of the first embodiment. Also in the second joint 33, similarly to the first joint 13, in the fourth pipe portion of the third pipe, the thirteenth locking portion of the seventh pipe portion and the fourteenth locking portion of the eighth pipe portion. A fourth joint member having a fifteenth locking portion corresponding to the thirteenth locking portion and a sixteenth locking portion corresponding to the fourteenth locking portion between the first and second portions through the gasket. And the tip of the eighth tube part are joined.

  That is, the seventh pipe portion of the third pipe, the eighth pipe portion of the third pipe, the thirteenth locking portion, the fourteenth locking portion, the fifteenth locking portion, and the sixteenth locking portion in the second joint 33. 10 are the first pipe portion 10ba (fifth pipe portion), the first pipe portion 10bb (sixth pipe portion), the ninth locking portion F9, and the tenth locking portion, respectively. This corresponds to F10, the eleventh locking portion F11, and the twelfth locking portion F12.

(Embodiment 4)
Another embodiment of the method for growing a group III nitride crystal according to the present invention is a method for growing a group III nitride crystal using the growth apparatus according to the third embodiment with reference to FIG. Disposing a raw material 6 containing at least one element selected from the group consisting of an alkali metal element and an alkaline earth metal element and a group III metal element, and the interior of the first and second pipes 10 and 20 The method includes a step of evacuating and a step of supplying the nitrogen source gas 9 into the reaction vessel 1. In the step of evacuating or supplying the nitrogen source gas 9, the airtightness of the first hermetic partition 10 d is the reaction vessel 1. And the nitrogen source gas supply device 7 side (i.e., the first vacuum exhaust device 8 side) is broken by the pressure difference between the second gas tight partition 30d and the reaction vessel 1 in the step of supplying the nitrogen source gas 9. ~ side It is broken by the pressure difference between the atmosphere side (the side opposite to the reaction vessel 1).

  Before the growth of the group III nitride crystal, the first hermetic partition 11d keeps the reaction vessel 1 airtight before the growth of the group III nitride crystal. When the airtightness of the first airtight partition 11d is broken in the evacuation process, the gas remaining in the first and second pipes 10, 20 and the reaction vessel 1 is efficiently removed by the evacuation process. The Further, when the airtightness of the first airtight partition 11d is broken in the step of supplying the nitrogen source gas after the step of evacuating, the first and second pipes 10 and 20 remain in the step of evacuating. Gas is removed very efficiently.

  Further, when the nitrogen source gas 9 is supplied to the reaction vessel 1, the airtightness of the second hermetic partition 30 d is broken, so that a new group is continuously introduced into the reaction vessel 1 during the growth of the group III nitride crystal. Nitrogen source gas 9 is supplied to flow out the unreacted gas inside the reaction vessel 1 and the residual gas after the reaction and impurities contained therein, and the atmospheric gas in the pressure vessel 5 containing oxygen or moisture Mixing in the reaction vessel 1 can be prevented, and a high group III nitride crystal can be obtained.

  Referring to FIG. 2, the group III nitride crystal growth method of the present embodiment includes the following steps. First, referring to FIG. 9B, the inside of the reaction vessel 1 in which the pipe part 10a (first pipe part) of the first pipe and the pipe part 30a (third pipe part) of the third pipe are connected. A raw material 6 containing at least one element selected from the group consisting of an alkali metal element and an alkaline earth metal element and a group III metal element is placed in the crucible 2 (placement step of the raw material in the reaction vessel). It is preferable to perform the raw material arrangement step in the reaction vessel in a nitrogen gas or argon gas atmosphere of 1 atm (100 kPa) dried in the drying vessel in order to prevent oxygen or moisture from being mixed into the raw material 6. Moreover, it is preferable that the water concentration in a dry container is 1.0 ppm or less, and it is more preferable that it is 0.54 ppm or less.

  Here, the other end of the tube portion 10a (first tube portion) whose one end is connected to the reaction vessel 1 is connected to one end of the joint 11 having the first hermetic partition provided with the first hermetic partition 11d. The other end of the airtight partition joint 11 is connected to one end of the tube portion 10ba (fifth tube portion). Further, the other end of the tube portion 30a (third tube portion) that is connected to the reaction vessel 1 at one end is connected to one end of the second airtight partition joint 31 including the second airtight partition 31d, and the second The other end of the joint 31 with the airtight partition is connected to one end of the pipe part 30ba (seventh pipe part).

  Next, the reaction vessel 1 in which the raw material 6 is arranged is accommodated in a predetermined position in a pressure vessel 5 provided with a heater 3 and a heat insulating material 4 (accommodating step of the reaction vessel into the pressure vessel). At this time, the reaction vessel 1 is hermetically sealed by the first hermetic partition 11d and the second hermetic partition 31d.

  Next, the other end of the pipe part 10ba (fifth pipe part) whose one end is connected to the first airtight partition joint 11 is connected to the pipe part 10bb (sixth pipe) of the first pipe by the first joint 13. Connect to one end of the tube. Further, the other end of the pipe portion 30ba (seventh pipe portion), one end of which is connected to the second airtight partition joint 31, is connected to the pipe portion 30bb (eighth of the third pipe 30) by the second joint 33. Connect to one end of the tube.

  Here, the other end of the pipe part 10bb (sixth pipe part) is connected to the nitrogen source gas supply device 7 via a valve 7v. In addition, one end of the second pipe 20 is connected to the middle of the pipe part 10bb (sixth pipe part) (joint part 10j between the first pipe 10 and the second pipe 20), and the other of the second pipe 20 The end is connected to the first vacuum exhaust device 8 through a valve 8v. Furthermore, the other end of the pipe part 30bb (eighth pipe part) of the third pipe 30 is drawn out into the atmosphere.

  That is, by connecting the pipe part 10ba (fifth pipe part) and the pipe part 10bb (sixth pipe part) by the first joint 13, the reaction vessel 1 and the nitrogen source gas supply device 7 are connected by the first pipe 10. The reaction vessel 1 and the first vacuum exhaust device 8 are connected by the second pipe 20. Furthermore, the third pipe 30 is drawn out from the reaction vessel 1 into the atmosphere by connecting the pipe part 30ba (seventh pipe part) and the pipe part 30bb (eighth pipe part) with the second joint 33.

  Next, the inside of the first and second pipes 10 and 20 is evacuated by the first evacuation apparatus 8 (evacuation process). At this time, when the airtightness of the first hermetic partition 11d is designed to be broken by a pressure of 1 atm (100 kPa) or less, the airtightness of the first hermetic partition 11d is the same as that of the reaction vessel 1 and nitrogen. It is broken by the pressure difference from the source gas supply device 7 side (that is, the first vacuum exhaust device 8 side). In such a case, the airtightness of the first airtight partition 11d is broken by the evacuation process, and the residual gas of the first and second pipes 10 and 20 and the reaction vessel 1 and the oxygen or moisture contained therein are efficiently removed. it can.

  In addition, when the airtightness of the first airtight partition 11d is designed to be broken at a pressure higher than 1 atm (100 kPa), the airtightness of the first airtight partition 11d is Is not broken, and during the subsequent supply of the nitrogen source gas 9 to the reaction vessel 1, due to the pressure difference between the reaction vessel 1 side and the nitrogen source gas supply device 7 side (that is, the first vacuum exhaust device 8 side) Removed. In such a case, the gas remaining in the first and second pipes 10 and 20 and the oxygen or moisture contained therein are removed very efficiently by the evacuation process. For this reason, mixing of oxygen or moisture into the reaction vessel 1 is prevented.

  On the other hand, if the airtightness of the second airtight partition 31d is broken in the evacuation process, the atmosphere enters the reaction vessel 1 from the third pipe 30 and oxygen and moisture in the atmosphere are used as raw materials. 6 will be mixed. For this reason, the airtightness of the second airtight partition 31d is designed so as not to be broken at a pressure of 1 atm (100 kPa).

  Next, the nitrogen source gas 9 is supplied from the nitrogen source gas supply device 7 into the reaction vessel 1 through the first pipe 10 (nitrogen source gas supply step). The nitrogen source gas is not particularly limited, but nitrogen gas is preferable from the viewpoint of growing a high-purity group III nitride crystal. At least selected from the group consisting of alkali metal elements and alkaline earth metal elements by heating the raw material 6 disposed in the crucible 2 of the reaction vessel 1 by the heater 3 together with the supply of the nitrogen raw material gas 9 to the reaction vessel 1. A melt containing one kind of element and a group III metal element is used. The group III nitride crystal grows by dissolving the nitrogen source gas 9 in the raw material 6 which is the melt. Such a group III nitride crystal has a high physical property because it is grown in the reaction vessel 1 from which oxygen or moisture is efficiently removed and mixing of oxygen or moisture is prevented.

  In the nitrogen source gas supply step, the airtightness of the second airtight partition 31d of the third pipe 30 is removed by a pressure difference between the reaction vessel 1 side and the atmosphere side (the side opposite to the reaction vessel 1). Therefore, the second hermetic partition is designed to be broken at a pressure lower than the nitrogen source gas pressure (usually about 2 to 7.5 MPa) during crystal growth. For example, the second hermetic partition 31d is designed so that the pressure resistance is 0.5 MPa.

  In this way, by supplying the nitrogen source gas 9 to the reaction vessel 1 and breaking the hermeticity of the second hermetic partition 31d, new nitrogen gas is continuously added to the reaction vessel 1 during the growth of the group III nitride crystal. Nitrogen gas 9 is supplied to flow out unreacted gas inside the reaction vessel 1 and residual gas after the reaction and impurities contained therein, and atmosphere gas in the pressure vessel 5 containing oxygen or moisture Can be prevented from being mixed into the reaction vessel 1, and a group III nitride crystal having higher physical properties can be grown.

(Embodiment 5)
Still another embodiment of the III-nitride crystal manufacturing apparatus according to the present invention is described with reference to FIG. 3 in that the second evacuation device 81 and the third piping 30 are added to the manufacturing apparatus of the third embodiment. The valve 30v formed in the middle of the outer side of the pressure vessel 5, the pipe portion 30bb between the second hermetic partition 31d of the third pipe 30 and the valve 30v, and the second vacuum exhaust device 81 are connected. A fourth pipe 40, and when the inside of the third and fourth pipes 30 and 40 is evacuated or when the nitrogen source gas 9 is supplied to the reaction vessel 1, the airtightness of the second airtight partition 31d The property is broken by the pressure difference between the reaction vessel 1 side and the atmospheric side (the side opposite to the reaction vessel 1).

  A valve 30v is formed in the middle of the pressure vessel 5 of the third pipe 30 and the fourth pipe 40 is connected to the pipe portion 30bb between the second hermetic partition 31d of the third pipe 30 and the valve 30v. By connecting the two evacuation devices 81, the inside of the third and fourth pipes 30 and 40 can be evacuated. Here, the material of the fourth pipe 40 is not particularly limited, but is preferably the same as that of the first, second, and third pipes.

  In the present embodiment, when the airtightness of the second airtight partition 31d is designed to be broken at a pressure higher than 1 atm (100 kPa), the inside of the third and fourth pipes 30 and 40 is evacuated. can do. When the airtightness of the second airtight partition 31d is designed to be broken at a pressure lower than 1 atm (100 kPa), the inside of the reaction vessel 1 is evacuated together with the inside of the third and fourth pipes 30 and 40. Can be exhausted. In these cases, the inside of the first and second pipes 10 and 20 is preferably evacuated by the first evacuation device 8.

  Further, when the first hermetic partition 11d and the second hermetic partition 31d are designed to be broken at a pressure smaller than 1 atm (100 kPa), the inside of the third and fourth pipes 30 and 40, the reaction The inside of the container 1 and the insides of the first and second pipes 10 and 20 can be evacuated. As described above, the residual gas and oxygen or moisture contained in the third and fourth pipes 30 and 40, the first and second pipes 10 and 20, and / or the reaction vessel 1 are efficiently removed. The

(Embodiment 6)
Still another embodiment of the Group III nitride crystal growth method according to the present invention is a Group III nitride crystal growth method using the growth apparatus of Embodiment 5 with reference to FIG. A step of disposing a raw material 6 containing at least one element selected from the group consisting of an alkali metal element and an alkaline earth metal element and a group III element, and the inside of the first and second pipes 10 and 20 At least one of a first evacuation step for evacuation and a second evacuation step for evacuating the inside of the third and fourth pipes 30 and 40, and a nitrogen source gas in the reaction vessel 1 9, and in the first evacuation step or the step of supplying the nitrogen source gas 9, the airtightness of the first hermetic partition 11 d is determined so that the reaction vessel 1 side and the nitrogen source gas supply device 7 side (that is, 1 in the second evacuation device 8 side), and the second gas evacuation step or the step of supplying the nitrogen source gas 9 causes the second gas-tight partition 31d to have an airtightness between the reaction vessel 1 side and the atmosphere side ( It is broken by the pressure difference between the reaction vessel 1 and the opposite side.

  The inside of the first and second pipes 10 and 20 can be evacuated by maintaining the airtightness of the first airtight partition 11d in the first evacuation process. Moreover, the inside of the 3rd and 4th piping 30 and 40 can be evacuated because the airtightness of the 2nd airtight partition 31d is maintained in a 2nd evacuation process.

  Further, since the airtightness of the first airtight partition 11d is broken in the first vacuum exhausting step, the inside of the reaction vessel 1 can be vacuum exhausted together with the inside of the first and second pipes 10 and 20. Further, the airtightness of the second hermetic partition 31d is broken in the second vacuum exhausting step, so that the inside of the reaction vessel 1 can be vacuum exhausted together with the third and fourth pipes 30 and 40. Further, the first and second pipes are broken by breaking the airtightness of the first airtight partition 11d and the second airtight partition 31d by at least one of the first vacuum exhausting step and the second vacuum exhausting step. The inside of 10, 20, the inside of the third and fourth pipes 30, 40, and the inside of the reaction vessel 1 can be evacuated.

  Further, in the step of supplying the nitrogen source gas 9, the nitrogen source gas 9 is supplied to the reaction vessel 1 by breaking the hermeticity of the first hermetic partition 11d, and furthermore, the second hermetic partition 31d has the hermeticity. By being broken, the unreacted gas in the reaction vessel 1 and the residual gas after the reaction and impurities contained in them can be discharged.

(Embodiment 7)
Still another embodiment of the group III nitride crystal production apparatus according to the present invention is shown in FIG. 4 in the production apparatus of the third embodiment, in the middle of the third pipe 30 on the outside of the pressure vessel 5. A fourth pipe 40 connecting the formed valve 30v, the pipe part 30bb between the second airtight partition 31d of the third pipe 30 and the valve 30v and the pipe part in the middle of the second pipe 20; And when the inside of the first, second, third and fourth pipes 10, 20, 30, 40 is evacuated or when the nitrogen source gas 9 is supplied to the reaction vessel 1, the second airtightness is provided. The airtightness of the partition 31d is broken by the pressure difference between the reaction vessel 1 side and the atmosphere side (the side opposite to the reaction vessel 1).

  A valve 30v is formed in the middle of the pressure vessel 5 of the third pipe 30 and the middle of the second pipe 20 and the pipe portion 30bb between the second airtight partition 31d of the third pipe 30 and the valve 30v. By forming the fourth pipe 40 that connects the first pipe part, the inside of the first, second, third, and fourth pipes 10, 20, 30, and 40 can be evacuated.

  In the present embodiment, when the airtightness of the first airtight partition 11d and the second airtight partition 31d is designed to be broken at a pressure greater than 1 atm (100 kPa), the first, second and third And the inside of the 4th piping 30 and 40 can be evacuated. When the airtightness of the first airtight partition 11d or the second airtight partition 31d is designed to be broken at a pressure smaller than 1 atm (100 kPa), the first, second, third and fourth pipes The inside of the reaction vessel 1 can be evacuated together with the inside of 10, 20, 30, 40. As described above, the residual gas and oxygen or moisture contained in the third and fourth pipes 30 and 40, the first and second pipes 10 and 20, and / or the reaction vessel 1 are efficiently removed. The

(Embodiment 8)
Still another embodiment of the Group III nitride crystal growth method according to the present invention is a Group III nitride crystal growth method using the growth apparatus of Embodiment 7 with reference to FIG. A step of disposing a raw material 6 containing at least one element selected from the group consisting of an alkali metal element and an alkaline earth metal element and a group III element, and first, second, third and fourth pipes And evacuating the inside 10, 20, 30, 40, and supplying the nitrogen source gas 9 into the reaction vessel 1, the first step in the step of evacuating or supplying the nitrogen source gas 9 The airtightness of the airtight partition 11d is broken by the pressure difference between the reaction vessel 1 side and the nitrogen source gas supply device 7 side (that is, the first vacuum exhaust device 8 side), and the vacuum source or nitrogen source gas 9 is supplied. In the process Airtightness of the second hermetic partition 31d is broken by the pressure difference between the reaction vessel 1 side and the atmosphere side (the reaction vessel 1 opposite) Te.

  In the evacuation step, the inside of the first and second pipes 10 and 20 can be evacuated by maintaining the airtightness of the first airtight partition 11d and the second airtight partition 31d. In the evacuation step, the inside of the reaction vessel 1 is evacuated together with the insides of the first and second pipes 10 and 20 by breaking the airtightness of the first airtight partition 11d or the second airtight partition 31d. Can be exhausted.

  Further, in the step of supplying the nitrogen source gas 9, the nitrogen source gas 9 is supplied to the reaction vessel 1 by breaking the hermeticity of the first hermetic partition 11d, and furthermore, the second hermetic partition 31d has the hermeticity. By being broken, the unreacted gas in the reaction vessel 1 and the residual gas after the reaction and impurities contained in them can be discharged.

  The embodiment disclosed this time should be considered as illustrative in all points and not restrictive. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

It is a schematic sectional drawing which shows one Embodiment of the manufacturing apparatus of the group III nitride crystal concerning this invention. It is a schematic sectional drawing which shows other embodiment of the manufacturing apparatus of the group III nitride crystal concerning this invention. It is a schematic sectional drawing which shows other embodiment of the manufacturing apparatus of the group III nitride crystal concerning this invention. It is a schematic sectional drawing which shows other embodiment of the manufacturing apparatus of the group III nitride crystal concerning this invention. It is a schematic sectional drawing which shows an example of the partition used for this invention. Here, (a) shows a state where the partition is held, and (b) shows a state where the partition is removed. It is a schematic sectional drawing which shows an example of the partition and filter used for this invention. It is a schematic sectional drawing which shows an example of the joint with a partition used for this invention. It is a schematic sectional drawing which shows the other example of the partition used for this invention. Here, (a) shows what bent a part of piping into the ring shape, (b) shows what bent a part of piping into the U-shape. It is a schematic sectional drawing which shows the reaction container with which the piping used for this invention is connected. Here, (a) shows a reaction vessel in which a part of the first piping is connected, and (b) shows a reaction vessel in which a part of the first and third pipings are connected. It is a schematic sectional drawing which shows an example of the coupling used for this invention.

Explanation of symbols

  1 reaction vessel, 2 crucible, 3 heater, 4 heat insulating material, 5 pressure vessel, 6 raw material, 7 nitrogen raw material gas supply device, 7v, 8v, 81v valve, 8 first vacuum exhaust device, 9 nitrogen raw material gas, 10 first 1 pipe, 10a, 10b, 10ba, 10bb, 30a, 30b, 30ba, 30bb pipe part, 10j joint part, 11 first joint with airtight partition, 11c first joint member, 11d first airtight partition, 11s , 13s gasket, 12a, 12b, 32a, 32b filter, 13 first joint, 13c third joint member, 20 second pipe, 30 third pipe, 31 second joint with airtight partition, 31d second Airtight partition, 33 second joint, 40 fourth piping, 81 second vacuum exhaust device, F1 first locking portion, F2 second locking portion, F3 third engagement Parts, the fourth locking portion F4, F9 ninth locking portion, F10 tenth locking portion, F11 11 engaging portion, F12 twelfth engaging portion.

Claims (16)

A reaction vessel, a pressure vessel containing the reaction vessel, a nitrogen source gas supply device, a first vacuum exhaust device, and the reaction vessel and the nitrogen source gas supply device penetrating a wall of the pressure vessel. A first piping connected, a first hermetic partition formed in the middle of the pressure vessel of the first piping, the nitrogen source gas supply device of the first piping, and the first piping A second pipe connecting the pipe portion between the airtight partition and the first vacuum exhaust device,
The reaction vessel is hermetically sealed by the first hermetic partition, and the first and second pipes are evacuated or supplied with nitrogen source gas into the reaction vessel. An apparatus for growing a group III nitride crystal in which the hermeticity of the hermetic partition is broken by a pressure difference between the reaction vessel side and the nitrogen source gas supply apparatus side.   The group III nitride crystal growth apparatus according to claim 1, wherein the first hermetic partition is a thin film.   The group III nitride crystal growth apparatus according to claim 2, wherein a filter is provided on at least one side of the first hermetic partition in the first pipe.   The first hermetic partition is formed between the first engagement portion of the first pipe portion of the first pipe and the second engagement portion of the second pipe portion of the first pipe. The group III of Claim 2 or Claim 3 fixed by the 1st joint member which has the 3rd latching | locking part corresponding to a latching | locking part, and the 4th latching | locking part corresponding to the said 2nd latching | locking part. Nitride crystal growth equipment.   The group III nitride crystal growth apparatus according to claim 1, wherein the first hermetic partition is a liquid. A third pipe extending from the reaction vessel through the wall of the pressure vessel to the atmosphere, and a second airtight partition formed midway on the inner side of the pressure vessel of the third pipe And further comprising
The reaction vessel is hermetically sealed by the second hermetic partition, and when supplying the nitrogen source gas to the reaction vessel, the second hermetic partition has an airtightness between the reaction vessel side and the atmosphere side. The III-nitride crystal growth apparatus according to any one of claims 1 to 5, wherein the growth apparatus is broken by a pressure difference. A second vacuum evacuation device, a valve formed midway outside the pressure vessel of the third pipe, and a pipe section between the second hermetic partition of the third pipe and the valve And a fourth pipe connecting the second vacuum exhaust device,
When the inside of the third and fourth pipes is evacuated or when the nitrogen raw material gas is supplied to the reaction vessel, the airtightness of the second hermetic partition is determined between the reaction vessel side and the atmosphere side. The group III nitride crystal growth apparatus according to claim 6, which is broken by a pressure difference. A valve formed midway outside the pressure vessel of the third pipe, a pipe section between the second hermetic partition of the third pipe and the valve, and a middle of the second pipe And a fourth pipe connecting the pipe part of
When the inside of the first, second, third and fourth pipes is evacuated or when the nitrogen source gas is supplied to the reaction vessel, the airtightness of the second hermetic partition is determined to be the reaction vessel side. The apparatus for growing a group III nitride crystal according to claim 6, which is broken by a pressure difference between the atmospheric pressure side and the atmospheric side.   9. The group III nitride crystal growth apparatus according to claim 6, wherein the second hermetic partition is a thin film.   The group III nitride crystal growth apparatus according to claim 9, wherein a filter is provided on at least one side of the second hermetic partition in the third pipe.   The second hermetic partition is formed between the fifth engagement portion of the third pipe portion of the third pipe and the sixth engagement portion of the fourth pipe portion of the third pipe. The group III of Claim 9 or Claim 10 fixed by the 2nd joint member which has the 7th latching | locking part corresponding to a latching | locking part, and the 8th latching | locking part corresponding to the said 6th latching | locking part. Nitride crystal growth equipment.   The III-nitride crystal growth apparatus according to any one of claims 6 to 8, wherein the second hermetic partition is a liquid. A method for growing a group III nitride crystal using the growth apparatus of claim 1, comprising:
Disposing a raw material containing at least one element selected from the group consisting of an alkali metal element and an alkaline earth metal element and the group III element in the reaction vessel; and inside the first and second pipes Evacuating and supplying a nitrogen source gas into the reaction vessel,
In the step of evacuating or the step of supplying the nitrogen source gas, the group III nitride crystal in which the airtightness of the first hermetic partition is broken by the pressure difference between the reaction vessel side and the nitrogen source gas supply device side Growth method. A method for growing a group III nitride crystal using the growth apparatus of claim 6, comprising:
Disposing a raw material containing at least one element selected from the group consisting of an alkali metal element and an alkaline earth metal element and the group III element in the reaction vessel; and inside the first and second pipes Evacuating and supplying a nitrogen source gas into the reaction vessel,
In the step of evacuating or supplying the nitrogen source gas, the airtightness of the first hermetic partition is broken by a pressure difference between the reaction vessel side and the nitrogen source gas supply side, and the nitrogen source gas is A method for growing a group III nitride crystal in which the airtightness of the second airtight partition is broken by a pressure difference between the reaction vessel side and the atmosphere side in the supplying step. A method for growing a group III nitride crystal using the growth apparatus of claim 7,
Disposing a raw material containing at least one element selected from the group consisting of an alkali metal element and an alkaline earth metal element and the group III element in the reaction vessel; and inside the first and second pipes At least one of a first evacuation step and a second evacuation step for evacuating the interior of the third and fourth pipes, and a nitrogen source gas in the reaction vessel. A process of supplying,
In the first evacuation step or the step of supplying the nitrogen source gas, the hermeticity of the first hermetic partition is broken due to a pressure difference between the reaction vessel side and the nitrogen source gas supply device side, A method for growing a group III nitride crystal in which the airtightness of the second hermetic partition is broken by a pressure difference between the reaction vessel side and the atmosphere side in a second evacuation step or a step of supplying the nitrogen source gas. A method for growing a group III nitride crystal using the growth apparatus according to claim 8, comprising:
Disposing a raw material containing at least one element selected from the group consisting of an alkali metal element and an alkaline earth metal element and the group III element in the reaction vessel, the first, second, third and A step of evacuating the inside of the fourth pipe, and a step of supplying a nitrogen source gas into the reaction vessel,
In the step of evacuating or supplying the nitrogen source gas, the hermeticity of the first hermetic partition is broken by a pressure difference between the reaction vessel side and the nitrogen source gas supply device side, and the step of evacuating is performed. Alternatively, in the step of supplying the nitrogen source gas, a Group III nitride crystal growth method in which the airtightness of the second airtight partition is broken by a pressure difference between the reaction vessel side and the atmosphere side.

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