CN101383279B - HVPE reactor for preparing nitride semiconductor substrate - Google Patents
HVPE reactor for preparing nitride semiconductor substrate Download PDFInfo
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- CN101383279B CN101383279B CN2008101676213A CN200810167621A CN101383279B CN 101383279 B CN101383279 B CN 101383279B CN 2008101676213 A CN2008101676213 A CN 2008101676213A CN 200810167621 A CN200810167621 A CN 200810167621A CN 101383279 B CN101383279 B CN 101383279B
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Abstract
The invention discloses an HVPE reactor which is convenient for adding and replacing a metal reactant and is used for preparing a nitride semiconductor substrate. The HVPE reactor comprises a boat body, a chlorine hydride inlet pipe, an ammonia gas inlet pipe, a metal chloride air inlet pipe and a foreign base seat, wherein the boat body can be divided into two parts and is convenient for replacing the metal reactant in the boat body, and the structure of the ammonia gas inlet pipe ensures not to block the division when the boat body is divided into the two parts; the metal chloride air inlet pipe adopts a single pipeline structure; after ammonia gas leaves the boat body, the ammonia gas inlet pipe is divided into a plurality of branch pipes which surround the metal chloride air inlet pipe, a certain distance is maintained between the branch pipes of the ammonia gas inlet pipe and the metal chloride air inlet pipe near a foreign substrate which is arranged on the foreign base seat to block the earlier mixture of the ammonia gas and the metal chloride so as to be favorable for reducing the parasitical aggradation of each pipe hole.
Description
Technical field
The invention belongs to hydride vapour phase epitaxy method (Hydride Vapor Phase Epitaxy is called for short HVPE) reactor technology field, relate in particular to a kind of growth apparatus with HVPE method growing nitride Semiconductor substrate.
Background technology
In recent years, III/V family wide bandgap compound semiconductor is receiving more and more people's attention.Gallium nitride (GaN) conduct representative wherein has physical characteristic and chemical stabilities such as high saturated electrons migration velocity, high breakdown electric field, forbidden band broad, and these characteristics make it become the ideal material of preparation great power LED, LD, HEMT, ultraviolet detector.
Because great power LED, LD are higher to the quality requirement of GaN crystal in preparation, so GaN self-supporting substrate just becomes the ideal platform of extension high-quality GaN.As adopt the high pressure dissolution method of standard; Because the very high temperature and the nitrogen pressure of growth needs of high-quality GaN; The vapour pressure of nitrogen has surpassed 6GPa at the equilibrium melting point place of gallium nitride; And lower growth rate has also limited large-scale production, so at present only do the minority mechanism of representative in the research of carrying out in this respect with the high-pressure physics of Poland.Metal-organic chemical vapor deposition equipment method (MOCVD) that present stage is widely used and molecular number epitaxy (MBE) method are also because growth rate is lower, thereby it is also comparatively difficult to prepare high-quality thick film gallium nitride self-supporting substrate.In addition, methods such as ammonia heat, electrolysis also just are in experimental stage at present.
Hydride vapour phase epitaxy method is the method that is used to growing gallium nitride the earliest, but because its growth rate is fast, can't the growing high-quality SQW etc. meticulous device architecture, promptly substituted afterwards by methods such as MOCVD, MBE.Yet just because of its have that growth rate is fast, equipment is simple, be convenient to realize advantage such as volume production, is paid attention to again by people again in recent years, becomes the prefered method of nitride such as preparation gallium nitride.
The common hvpe reactor device that is used to prepare the nitride-based semiconductor substrate comprises the vertical hanging structure and is inverted supporting construction; Wherein the vertical hanging structure is as shown in Figure 1, and it comprises boat body 1, foreign substrate pedestal 2, quartz wall 3, ammonia air inlet pipe, metal chloride snorkel, hydrogen chloride air inlet pipe and tail gas exhaust outlet etc.Wherein boat body 1 is used to put metal reactant; This metal reactant generates metal chloride gas with the hcl reaction that feeds boat body 1; This metal chloride gas arrives via the metal chloride snorkel and places foreign substrate place and the ammonia gas react on the said foreign substrate pedestal 2, thus can be on foreign substrate the growing metal nitride.It is as shown in Figure 2 that it is inverted supporting construction, and the difference of being inverted supporting construction and vertical hanging structure is that the foreign substrate pedestal 2 of vertical hanging structure is positioned at the bottom of reactor, 1 top that is positioned at this foreign substrate pedestal 2 of boat body; The foreign substrate pedestal 2 of being inverted supporting construction then is positioned at the top of reactor, 1 top that is positioned at this foreign substrate pedestal 2 of its boat body.
But the HVPE equipment for preparing the nitride-based semiconductor substrate does not at present also reach optimization, and the problem of its existence mainly comprises: the replacing of metal reactant is very complicated time-consuming in the reactor; Nitride is prone on reactor, produce parasitic deposition, thereby influences the growth of nitride, and reactor lifetime is shortened.Therefore,, further improve the uniformity of reacting gas utilance and nitride thickness, need do further to optimize growth apparatus in order to make HVPE equipment more succinctly, efficiently.
Summary of the invention
The technical problem that the present invention will solve provides a kind of hvpe reactor device that is used to prepare the nitride-based semiconductor substrate of being convenient to add and change metal reactant.
For solving the problems of the technologies described above, the hvpe reactor device that the present invention is used to prepare the nitride-based semiconductor substrate comprises:
Boat body, hydrogen chloride air inlet pipe, ammonia air inlet pipe, metal chloride snorkel and foreign substrate pedestal;
Wherein, said boat body is used to hold metal reactant, and this boat body can be split as two parts, so that add and replacing metal reactant wherein;
Said hydrogen chloride air inlet pipe is used for introducing hydrogen chloride gas and reacts to said boat body and metal reactant; Thereby generate metal chloride gas, this metal hydrogen chloride gas is taken to the foreign substrate place that places on the said foreign substrate pedestal by said metal chloride snorkel;
Said ammonia air inlet pipe is used to introduce ammonia to the foreign substrate place that places on the said foreign substrate pedestal, with said metal chloride gas reaction growing nitride; The structure of said ammonia air inlet pipe should guarantee to be split as two-part the time at said boat body that it can not hinder this fractionation.The change of can stretching of the length of for example said ammonia air inlet pipe, for example it is a flexible pipe again, perhaps it comprises two parts pipeline of separation, more for example its for being split as the rigidity pipe of two parts pipeline.And said ammonia air inlet pipe is preferably through said boat body.
Said metal chloride snorkel can adopt the single tube line structure, and after ammonia left the boat body, said ammonia air inlet pipe can be divided into some arms, be centered around said metal chloride snorkel around; Near the foreign substrate place that places on the said foreign substrate pedestal; Keep certain distance between each arm of said ammonia air inlet pipe and the said metal chloride snorkel; To stop ammonia to mix, help reducing the parasitic deposition at mouth of pipe place like this with the too early of metal chloride gas.
Said ammonia air inlet pipe specifically can be divided into three arms.
Hvpe reactor device of the present invention can adopt the vertical hanging structure, also can adopt the inversion supporting construction.
For the vertical hanging structure, said foreign substrate pedestal is positioned at the bottom of reactor, and said boat body, hydrogen chloride air inlet pipe, ammonia air inlet pipe and metal chloride snorkel all are positioned at the top of this foreign substrate pedestal.
For this vertical hanging structure, before ammonia left the boat body, said hydrogen chloride air inlet pipe and ammonia air inlet pipe can adopt sleeve structure, and wherein interior pipe feeds hydrogen chloride gas, and outer tube then feeds ammonia; This sleeve pipe lower nozzle can be flooded by the liquid reactant metal thing in the said boat body, thereby in the boat body, forms two air chambers of isolating each other, promptly interior air chamber and outer air chamber.
A kind of improvement as such scheme; Air chamber is in the air chamber of inner tubal wall and liquid level formation in said; The air inlet mouth of pipe top of said metal chloride snorkel hides has a umbrella-shaped structure; This umbrella-shaped structure is used to stop that hydrogen chloride gas gets into said metal chloride snorkel to avoid it, and metal chloride gas then can get into this snorkel from the air inlet mouth of pipe of said metal chloride snorkel.
Another kind as such scheme improves; Said ammonia air inlet pipe can be divided into two parts up and down; Its first half is the outer tube of said sleeve pipe; Its latter half is separated with the first half, and the air inlet mouth of pipe of the latter half of this ammonia air inlet pipe is positioned at said outer air chamber, and exceeds the liquid level of said metal reactant.Like this, in the air chamber, ammonia is not consumed basically outside said, can be directly the latter half through said ammonia air inlet pipe reach the foreign substrate place.
For being inverted supporting construction, said foreign substrate pedestal is positioned at the top of reactor, and said boat body, hydrogen chloride air inlet pipe, ammonia air inlet pipe and metal chloride snorkel all are positioned at the below of this foreign substrate pedestal.
Be inverted in the reactor of supporting construction at this, said boat body inside also has baffle plate, and this baffle plate is used for the liquid reactant metal thing, and boat body inside is divided into two air chambers of isolating each other, promptly interior air chamber and outer air chamber; Before ammonia left the boat body, said hydrogen chloride air inlet pipe and ammonia air inlet pipe adopted sleeve structure, and wherein interior pipe feeds hydrogen chloride gas, and interior pipe gets in the interior air chamber of said boat body, and exceeds the liquid level of metal reactant; Outer tube feeds ammonia, and outer tube gets in the outer air chamber of said boat body, and exceeds the liquid level of metal reactant.Said outer tube can be divided into some arms, for example three road arms.
Said hydrogen chloride air inlet pipe is that the upper end screening of the mouth of pipe of giving vent to anger of said interior pipe has a umbrella-shaped structure, in should managing with the metal nitride gas entering that stops growth.
Further, said ammonia air inlet pipe can be divided into two parts up and down, and its latter half is the outer tube of said sleeve pipe, and its latter half is separated with the first half, and the air inlet mouth of pipe of the first half of this ammonia air inlet pipe is positioned at said outer air chamber.
Beneficial effect of the present invention is:
The present invention is directed to hvpe reactor device that traditional being used to prepare the nitride-based semiconductor substrate and change the shortcoming of metal reactant difficulty and improve, the boat body can be split, thereby guaranteed the convenience that metal reactant adds and changes; Simultaneously, the present invention improves the reacting gas air feeder structure, greatly reduces the parasitic deposition at mouth of pipe place, thereby has improved the utilance of reacting gas, and the growth uniformity of nitride on foreign substrate.
Description of drawings
Fig. 1 is the vertical hanging structural representation that common being used to prepares the hvpe reactor device of nitride-based semiconductor substrate;
Fig. 2 is the inversion supporting construction sketch map of common the being used to hvpe reactor device for preparing the nitride-based semiconductor substrate;
Fig. 3 is the part-structure sketch map that adopts the hvpe reactor device of the present invention of vertical hanging structure;
Fig. 4 is the cutaway view of structure shown in Figure 3 along the AA line;
Fig. 5 is the part-structure sketch map that adopts the hvpe reactor device of the present invention of being inverted supporting construction;
Fig. 6 is the cutaway view of structure shown in Figure 5 along the CC line.
Embodiment
Below in conjunction with accompanying drawing, and with the gallium nitride semiconductor substrate be prepared as the example the present invention is explained further details.
Fig. 3 is the part-structure sketch map that adopts the hvpe reactor device of the present invention of vertical hanging structure; As shown in the figure, the hvpe reactor device that the present invention is used to prepare the nitride-based semiconductor substrate mainly comprises: boat body 1, hydrogen chloride air inlet pipe 4, ammonia air inlet pipe, metal chloride snorkel 7 and foreign substrate pedestal.
Said boat body 1 is that the gallium boat can be split as two parts, so that change gallium wherein.The latter half of gallium boat can be connected to the first half through modes such as knob or bayonet sockets.
In embodiments of the present invention, said ammonia air inlet pipe is divided into two parts up and down, and its first half and said hydrogen chloride air inlet pipe 4 form sleeve structure, and this sleeve pipe is fixed in the first half of gallium boat through flange.Wherein hydrogen chloride air inlet pipe 4 is the cover inner tube layer, and promptly pipe feeds hydrogen chloride gas in this sleeve pipe, and outer tube then feeds ammonia.As shown in Figure 3, after getting into the gallium boat, it is big that this sleeve pipe bore becomes, and when gallium liquid 8 was sealed the outlet of sleeve pipe, the internal strain of gallium boat became inside and outside two isolated each other air chambers like this.Through the temperature in the control gallium boat, hydrogen chloride and gallium can generate gallium chloride gas in the reaction of internal reaction chamber, and gallium chloride gas is that the gallium chloride snorkel arrives foreign substrate place and ammonia gas react via metal chloride snorkel 7, thereby obtains gallium nitride single crystal.The air inlet upper end of gallium chloride snorkel hides has a umbrella-shaped structure 9; When hydrogen chloride is that outer tube is when getting in the gallium boat air chamber from the cover outer tube layer; It is stopped by this umbrella-shaped structure 9 and around being diffused into, hydrogen chloride at first contacts with gallium liquid 8 like this, and at high temperature reacts with gallium fast and more fully; Having avoided the window of hydrogen chloride gas below this umbrella-shaped structure 9 is this snorkel of air inlet entering of metal chloride snorkel 7, thereby arrives the normal growth that the foreign substrate place influences gallium nitride.
The ammonia air inlet pipe then is divided into two parts up and down, and its first half is the outer tube of said sleeve pipe, and its latter half then is responsible for taking the ammonia in the outer air chamber of said gallium boat to the foreign substrate place.In the present embodiment, the gallium chloride snorkel adopts thinner single tube line structure, can increase the gallium chloride concentration on foreign substrate surface like this, improves the gallium chloride utilance; The latter half of ammonia air inlet pipe then is divided into three arms, and the latter half of ammonia air inlet pipe adopts the multitube structure, can make on the foreign substrate growth of gallium nitride more even.As shown in Figure 4, three arms 6 of ammonia air inlet pipe the latter half be centered around the gallium chloride snorkel around, adopt quartzy thin rod to fix between each arm and the gallium chloride snorkel, to prevent conduit failure as bracing frame.And; Between each arm and the gallium chloride snorkel certain distance is arranged; Can make the gallium chloride gas at each arm mouth of pipe place and the ammonia at gallium chloride snorkel mouth of pipe place all maintain a lower concentration like this; Stop ammonia to mix, thereby greatly reduce the parasitic deposition at each mouth of pipe place with the too early of gallium chloride.
Fig. 5 is the part-structure sketch map that adopts the hvpe reactor device of the present invention of being inverted supporting construction, and arrow is represented the path of hydrogen chloride gas among this figure.As shown in the figure, have baffle plate 11 in the gallium boat, this baffle plate is divided into two air chambers of isolating each other with gallium liquid with boat body inside, promptly interior air chamber and outer air chamber.
In the present embodiment; The ammonia air inlet pipe also is divided into two parts up and down, and its latter half 5 forms sleeve structure with hydrogen chloride air inlet pipe 4, and this sleeve pipe is positioned at the below of gallium boat; Pipe feeds hydrogen chloride wherein; Interior pipe gets into the interior air chamber of gallium boat, and its upper end, gas outlet also hides has a umbrella-shaped structure, this umbrella-shaped structure to be used for stopping that the gallium chloride gas that interior air chamber generates gets into this hydrogen chloride air inlet pipe 4; The outer tube of sleeve pipe feeds ammonia, and outer tube divides the outer air chamber of three tunnel entering gallium boats, and is as shown in Figure 6.And as shown in Figure 6, in embodiments of the present invention, can also feed in each gas piping with ammonia or hydrogen as carrier gas.
The first half of gallium chloride snorkel and ammonia air inlet pipe is positioned at the top of gallium boat; Wherein the gallium chloride snorkel adopts thinner single tube line structure; The first half of ammonia air inlet pipe then is divided into three arms; These three arms be centered around the gallium chloride snorkel around, adopt quartzy thin excellent bracing frame to fix between each arm and the gallium chloride snorkel.And, between each arm and the gallium chloride snorkel certain distance is arranged, mix with the too early of gallium chloride to stop ammonia.
The notion of the first half and the latter half among this paper should not be construed as gallium boat or ammonia air inlet pipe and is divided into two parts up and down.
Above-described specific embodiment; The object of the invention, technical scheme and beneficial effect have been carried out further explain; Institute it should be noted; The above is merely specific embodiment of the present invention, and those skilled in the art can carry out various changes and modification to the present invention and not break away from the spirit and scope of the present invention.Like this, belong within the scope of technical scheme and equivalent technologies thereof of claim record of the present invention if of the present invention these are revised with modification, then the present invention also is intended to comprise these changes and modification interior.
Claims (10)
1. a hvpe reactor device that is used to prepare the nitride-based semiconductor substrate comprises boat body, hydrogen chloride air inlet pipe, ammonia air inlet pipe, metal chloride snorkel and foreign substrate pedestal, and wherein, said boat body is used to hold metal reactant; Said hydrogen chloride air inlet pipe is used for introducing hydrogen chloride gas and reacts to said boat body and metal reactant; Thereby generate metal chloride gas, this metal hydrogen chloride gas is taken to the foreign substrate place that places on the said foreign substrate pedestal by said metal chloride snorkel; Said ammonia air inlet pipe is used to introduce ammonia to the foreign substrate place that places on the said foreign substrate pedestal, with said metal chloride gas reaction growing nitride; It is characterized in that:
Said boat body can be split as two parts, so that add and replacing metal reactant wherein;
The structure of said ammonia air inlet pipe should guarantee to be split as two-part the time at said boat body that it can not hinder this fractionation.
2. the hvpe reactor device that is used to prepare the nitride-based semiconductor substrate according to claim 1 is characterized in that:
Said ammonia air inlet pipe is through said boat body.
3. the hvpe reactor device that is used to prepare the nitride-based semiconductor substrate according to claim 1 is characterized in that:
Said metal chloride snorkel adopts the single tube line structure, and after ammonia left said boat body, said ammonia air inlet pipe was divided into some arms, be centered around said metal chloride snorkel around; Near the foreign substrate place that places on the said foreign substrate pedestal, keep certain distance between each arm of said ammonia air inlet pipe and the said metal chloride snorkel, mix with the too early of metal chloride gas to stop ammonia.
4. according to claim 1 or the 2 or 3 described hvpe reactor devices that are used to prepare the nitride-based semiconductor substrate, it is characterized in that:
This hvpe reactor device adopts the vertical hanging structure, that is: said foreign substrate pedestal is positioned at the bottom of reactor, and said boat body, hydrogen chloride air inlet pipe, ammonia air inlet pipe and metal chloride snorkel all are positioned at the top of this foreign substrate pedestal.
5. the hvpe reactor device that is used to prepare the nitride-based semiconductor substrate according to claim 4 is characterized in that:
Before ammonia left the boat body, said hydrogen chloride air inlet pipe and ammonia air inlet pipe adopted sleeve structure, and wherein interior pipe feeds hydrogen chloride gas, and outer tube then feeds ammonia;
Said sleeve pipe lower nozzle is flooded by the liquid reactant metal thing in the said boat body, thereby in the boat body, forms two air chambers of isolating each other, promptly interior air chamber and outer air chamber.
6. the hvpe reactor device that is used to prepare the nitride-based semiconductor substrate according to claim 5 is characterized in that:
In said in the air chamber; The air inlet mouth of pipe top of said metal chloride snorkel hides has a umbrella-shaped structure; This umbrella-shaped structure is used to stop that hydrogen chloride gas gets into said metal chloride snorkel to avoid it, and metal chloride gas then can get into this snorkel from the air inlet mouth of pipe of said metal chloride snorkel.
7. the hvpe reactor device that is used to prepare the nitride-based semiconductor substrate according to claim 5 is characterized in that:
Said ammonia air inlet pipe is divided into two parts up and down; Its first half is the outer tube of said sleeve pipe; Its latter half is separated with the first half, and the air inlet mouth of pipe of the latter half of this ammonia air inlet pipe is positioned at said outer air chamber, and exceeds the liquid level of said metal reactant.
8. according to claim 1 or the 2 or 3 described hvpe reactor devices that are used to prepare the nitride-based semiconductor substrate, it is characterized in that:
This hvpe reactor device adopts is inverted supporting construction, that is: said foreign substrate pedestal is positioned at the top of reactor, and said boat body, hydrogen chloride air inlet pipe, ammonia air inlet pipe and metal chloride snorkel all are positioned at the below of this foreign substrate pedestal.
9. the hvpe reactor device that is used to prepare the nitride-based semiconductor substrate according to claim 8 is characterized in that:
Said boat body inside also has baffle plate, and this baffle plate is used for the liquid reactant metal thing, and boat body inside is divided into two air chambers of isolating each other, promptly interior air chamber and outer air chamber; Before ammonia left the boat body, said hydrogen chloride air inlet pipe and ammonia air inlet pipe adopted sleeve structure, and wherein interior pipe feeds hydrogen chloride gas, and interior pipe gets in the interior air chamber of said boat body, and exceeds the liquid level of metal reactant; Outer tube feeds ammonia, and outer tube gets in the outer air chamber of said boat body, and exceeds the liquid level of metal reactant.
10. the hvpe reactor device that is used to prepare the nitride-based semiconductor substrate according to claim 9 is characterized in that:
Said sleeve pipe outer tube is divided into some arms.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008101676213A CN101383279B (en) | 2008-10-21 | 2008-10-21 | HVPE reactor for preparing nitride semiconductor substrate |
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| CN2008101676213A CN101383279B (en) | 2008-10-21 | 2008-10-21 | HVPE reactor for preparing nitride semiconductor substrate |
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| CN101383279A CN101383279A (en) | 2009-03-11 |
| CN101383279B true CN101383279B (en) | 2012-01-04 |
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| CN102465337B (en) * | 2010-11-18 | 2014-07-16 | 南京大学 | Multi-piece multi-source horizontal hydride vapor phase epitaxy growth system |
| CN105154969A (en) * | 2015-10-19 | 2015-12-16 | 中国电子科技集团公司第四十六研究所 | Single-crystal furnace cavity for improving uniformity of nitride grown by HVPE method |
| CN106238414B (en) * | 2016-07-30 | 2019-02-12 | 东莞市中镓半导体科技有限公司 | It is a kind of for cleaning the bracket of Source |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1779411A1 (en) * | 2004-06-30 | 2007-05-02 | Wang Nang Wang | Deposition technique for producing high quality compound semiconductor materials |
| JP2007314357A (en) * | 2006-05-23 | 2007-12-06 | Mitsubishi Chemicals Corp | Nitride semiconductor crystal and its manufacturing method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1779411A1 (en) * | 2004-06-30 | 2007-05-02 | Wang Nang Wang | Deposition technique for producing high quality compound semiconductor materials |
| JP2007314357A (en) * | 2006-05-23 | 2007-12-06 | Mitsubishi Chemicals Corp | Nitride semiconductor crystal and its manufacturing method |
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