CN212582032U - System for continuously growing large-size high-quality nitride single crystal by flux method - Google Patents
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Abstract
The utility model discloses a system for continuously growing large-size high-quality nitride single crystals by a fluxing agent method. The system comprises: the device comprises a reaction growth unit, a raw material supply unit, a waste recovery unit, a growth stagnation monitoring unit and a control unit, wherein the reaction growth unit comprises a reaction chamber for reacting and growing nitride single crystals, the raw material supply unit and the waste recovery unit are respectively connected with the reaction chamber, the waste recovery unit is at least used for guiding out waste materials in the reaction chamber, the growth stagnation monitoring unit is at least used for monitoring the growth state of the nitride single crystals, and the control unit is also connected with the raw material supply unit, the waste recovery unit and the growth stagnation monitoring unit. The system provided by the utility model has the raw material supply unit of automatic homogeneity supplementary raw materials, through in the growth process, constantly supplyes the growth raw materials, realizes the automatic continuous uniform growth of gallium nitride single crystal.
Description
Technical Field
The utility model relates to a system for flux method growth nitride single crystal, in particular to system for flux method continuous growth jumbo size high quality nitride single crystal belongs to crystal preparation technical field.
Background
The growth technology of obtaining gallium nitride (GaN) single crystal by Flux method (Na Flux method) is one of the internationally recognized growth methods for obtaining gallium nitride single crystal with low cost, high quality and large size. The general growth process of a bulk single crystal of gallium nitride is: selecting proper raw materials (mainly comprising gallium metal, sodium metal, carbon additive and the like) according to the component proportion, placing a crucible filled with growth raw materials and gallium nitride seed crystals in a growth furnace, and carrying out liquid phase epitaxy on the gallium nitride seed crystals to obtain gallium nitride body single crystals with different thicknesses by controlling different growth times under the nitrogen atmosphere with certain growth temperature and certain growth pressure. However, during the growth process, the gallium nitride single crystal grows and the growth raw material is consumed continuously (particularly, the gallium metal is consumed), until the liquid level of the growth raw material is lower than the epitaxial growth surface of the gallium nitride, and the growth stops.
In order to obtain a large-size gallium nitride single crystal, the growth time is effectively prolonged, along with the extension of the growth time, raw materials in a crucible are consumed, and the gallium nitride single crystal grows thick, so that on one hand, the liquid level of the growing raw materials is not high enough to cover the epitaxial growth surface of the gallium nitride, and the growth is stopped; on the other hand, the proportioning range of the raw materials in the growth system is deviated from the optimized proportioning range of the growth raw materials, so that the subsequent growth is unbalanced, the crystal quality is poor, and the growth speed deviates from the optimal growth state.
Therefore, how to realize the stable and continuous growth of the gallium nitride single crystal in the growth system is a technical problem to be solved urgently for obtaining the large-size high-quality gallium nitride single crystal.
SUMMERY OF THE UTILITY MODEL
The utility model mainly aims to provide a system for continuously growing large-size high-quality nitride single crystals by a fluxing agent method so as to overcome the defects in the prior art.
For realizing the purpose of the utility model, the utility model discloses a technical scheme include:
an embodiment of the utility model provides a system for flux method continuous growth jumbo size high quality nitride single crystal on the one hand, it includes: the device comprises a reaction growth unit, a raw material supply unit, a waste recovery unit, a growth stagnation monitoring unit and a control unit, wherein the control unit is respectively connected with the reaction growth unit, the raw material supply unit, the waste recovery unit and the growth stagnation monitoring unit;
the reaction growth unit comprises a reaction chamber for nitride single crystal reaction growth, the raw material supply unit and the waste material recovery unit are respectively communicated with the reaction chamber, the raw material supply unit is at least used for providing raw materials required by nitride single crystal growth for the reaction chamber, the waste material recovery unit is at least used for leading out waste materials in the reaction chamber,
the growth stagnation monitoring unit is at least used for monitoring the growth state of the nitride single crystal, an
The control unit is at least used for regulating and controlling the working states of the raw material supply unit and the waste recovery unit according to the monitoring signal of the growth stagnation monitoring unit.
The embodiment of the present invention provides a method for continuously growing large-sized high-quality nitride single crystal by flux method, which comprises:
providing a system for continuously growing large-size high-quality nitride single crystals by the flux method;
raw materials required for growing the nitride single crystal are filled in a reaction chamber of the reaction growth unit, and growth conditions are regulated and controlled to grow the nitride single crystal;
and monitoring the growth state of the nitride single crystal by a growth stagnation monitoring unit, and judging whether the waste material in the reaction chamber needs to be led out by a waste material recovery unit and/or the raw material required by the growth of the nitride single crystal needs to be input into the reaction chamber by a raw material supply unit according to the growth state, so that the nitride single crystal continuously grows to reach the required specification.
Further, the method for continuously growing the large-size high-quality nitride single crystal by the flux method specifically comprises the following steps: collecting intensity signals of a nitride characteristic peak in the reaction chamber by the X-ray growth monitoring device, obtaining a height difference value between the liquid level of the raw material in the reaction chamber and the epitaxial growth surface of the nitride single crystal according to the intensity signals of the nitride characteristic peak, and comparing the height difference value with a set threshold value so as to judge whether the growth of the nitride single crystal is stopped or not,
if so, leading out the waste in the reaction chamber by a waste recovery unit and/or inputting the raw materials required for growing the nitride single crystal into the reaction chamber by a raw material supply unit so as to continue growing the nitride single crystal, and if not, not starting the waste recovery unit and/or the raw material supply unit; preferably, if the growth of the nitride single crystal is stopped, the waste material in the reaction chamber is first taken out by the waste material recovery unit, and then the raw material required for growing the nitride single crystal is fed into the reaction chamber by the raw material supply unit, so that the nitride single crystal continues to grow.
Compared with the prior art, the utility model has the advantages that:
1) the system provided by the embodiment of the utility model is provided with a raw material supply unit for automatically and uniformly supplying raw materials, and realizes the automatic continuous and uniform growth of the gallium nitride single crystal by continuously supplying growth raw materials in the growth process;
2) the embodiment of the utility model provides a system and method for growing large-size high-quality nitride single crystal in succession of fluxing agent method still realizes the continuous replenishment of the raw materials that are used for growing the nitride single crystal in the reaction chamber through raw materials supply unit and waste recovery nitrogen source to guarantee the uniformity of ratio between the multiple raw materials that are used for growing the nitride single crystal, avoid the residual waste material in the reaction chamber to treat the problem that the ratio scope of supplying raw materials breaks away from the optimal growth ratio scope;
3) the embodiment of the utility model provides a system for growing jumbo size high quality nitride single crystal in succession of fluxing agent method, simple structure, operation and convenience simple to use.
Drawings
FIG. 1 is a schematic structural view of a system for continuously growing a large-sized high-quality nitride single crystal by a flux method according to an exemplary embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a system and method for continuously growing large-size high-quality nitride single crystals by a flux method according to an exemplary embodiment of the present invention;
FIG. 3 is a schematic flow chart of a method for continuously growing a large-sized high-quality nitride single crystal by a flux method according to an exemplary embodiment of the present invention;
fig. 4 is a schematic view of a nitride device structure fabricated using the system.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
In order to overcome the problems in the prior art, the embodiment of the invention provides a system and a method for continuously growing large-size high-quality nitride single crystals by a flux method, which realize continuous supplement of raw materials for growing the nitride single crystals in a reaction chamber and ensure consistency of proportioning among a plurality of raw materials for growing the nitride single crystals by a raw material supplement unit and a waste material recovery nitrogen source, and avoid the problem that the proportioning range of residual waste materials to raw materials to be supplied in the reaction chamber is separated from the optimized growth proportioning range.
In addition, the waste recovery unit can lead out the residual raw materials from the reaction chamber after the growth of the single crystal is finished so as to prevent the residual sodium metal and gallium metal from adhering to the gallium nitride single crystal, the gallium nitride single crystal is convenient to clean after being taken out, and the metal can be prevented from being solidified on the surface of the gallium nitride single crystal, and the gallium nitride single crystal is cracked due to larger stress in the cooling process caused by different thermal expansion coefficients, so that the high-quality and complete gallium nitride single crystal can be obtained.
Based on the relationship between the raw material ratio and the growth rate, the growth rate of gallium nitride single crystal grown by the fluxing agent method can be effectively improved by controlling and keeping the raw material ratio stable, and the content of the carbon additive has obvious influence on the polycrystalline generation inhibition effect of gallium nitride grown by the fluxing agent method, so that the recovery of the waste material is very important, the waste material is timely led out to realize the consistency of the raw material ratio, the faster growth rate is obtained, the gallium nitride growth efficiency is improved, the time cost of single crystal growth is reduced, and the generation of polycrystal and the adverse influence on the crystal quality are avoided.
According to the system for continuously growing the large-size high-quality nitride single crystal by the flux method, the growth stagnation monitoring unit is arranged in the growth system, the situation that the liquid level of the raw material is lower than the epitaxial growth surface of the gallium nitride single crystal is achieved, namely the raw material is supplemented in time through the raw material supplementing unit, the growth stagnation monitoring unit comprises the X-ray growth monitoring device, for example, when the growth is stopped, waste materials in the reaction chamber are led out through the waste material recycling unit, so that the proportion of the raw materials to be supplemented is not influenced by the components of the waste materials, then the raw materials with a certain proportion are automatically supplemented through the raw material supplementing unit, so that the high-efficiency automatic supplement of the raw materials is achieved, the stable and continuous growth of the gallium nitride single crystal is achieved, and finally the large-size uniform-.
Specifically, in the process of growing the gallium nitride single crystal by loading raw materials into a reaction chamber, acquiring an intensity signal of a characteristic peak of the gallium nitride in real time through an X-ray growth monitoring device, judging the intensity of the characteristic peak to obtain the height from the liquid level of the molten raw materials to the epitaxial growth surface of the gallium nitride single crystal, if the height is lower than a set threshold value, judging that the growth is stopped, sending a growth stop signal to a control unit, controlling a waste recovery unit to start waste recovery, and sucking out residual waste in the reaction chamber; after the waste recovery is finished, the control unit controls the raw material supplementing unit to automatically supply raw materials to the reaction chamber.
The embodiment of the invention provides a system for continuously growing large-size high-quality nitride single crystals by a fluxing agent method, wherein a molten liquid uniformity detection device (such as a flow meter) is arranged at a first flow guide pipe in a raw material supply unit to judge the uniformity of raw material supply, so that the raw material component distribution or uneven mixture ratio is prevented, the uniform supply of the growing raw material is ensured, and a stirring device in a raw material supply chamber is provided with a high-temperature alloy stirring blade to realize the corrosion-resistant effect of the stirring blade at high temperature.
Specifically, an aspect of the embodiments of the present invention provides a system for continuously growing a large-size high-quality nitride single crystal by a flux method, including: the device comprises a reaction growth unit, a raw material supply unit, a waste recovery unit, a growth stagnation monitoring unit and a control unit, wherein the control unit is respectively connected with the reaction growth unit, the raw material supply unit, the waste recovery unit and the growth stagnation monitoring unit;
the reaction growth unit comprises a reaction chamber for nitride single crystal reaction growth, the raw material supply unit and the waste material recovery unit are respectively communicated with the reaction chamber, the raw material supply unit is at least used for providing raw materials required by nitride single crystal growth for the reaction chamber, the waste material recovery unit is at least used for leading out waste materials in the reaction chamber,
the growth stagnation monitoring unit is at least used for monitoring the growth state of the nitride single crystal, an
The control unit is at least used for regulating and controlling the working states of the raw material supply unit and the waste recovery unit according to the monitoring signal of the growth stagnation monitoring unit.
Further, the raw material supply unit comprises at least one raw material supply chamber and at least one gas supply device, the raw material supply chamber is at least used for containing at least one raw material required by growing the nitride single crystal, and the raw material supply chamber is communicated with the reaction chamber through a feeding pipeline;
the gas supply device is communicated with the raw material supply chamber through a first gas guide pipeline and is at least used for providing inert gas for the raw material supply chamber, a first gas pressure difference is formed between the raw material supply chamber and the reaction chamber, and the raw material in the raw material supply chamber can be driven to flow into the reaction chamber by the first gas pressure difference.
Further, the raw material supply chamber is a sealed chamber.
Further, the feeding pipeline enters the reaction chamber from the bottom of the reaction chamber, and a discharge port of the feeding pipeline is far away from the epitaxial surface of the nitride single crystal.
Furthermore, a flow rate meter is arranged in the feeding pipeline and is at least used for monitoring the uniformity of the raw materials flowing through the feeding pipeline.
Further, a stirring device is also arranged in the raw material supply chamber; preferably, the stirring device is further connected with a rotating speed monitoring and adjusting device, and the rotating speed monitoring and adjusting device is further connected with the control unit.
Furthermore, the raw material supply unit comprises a plurality of raw material supply chambers, and the raw material supply chambers are respectively used for accommodating at least one raw material required for growing different structural layers of the nitride single crystal.
Further, the waste recovery unit comprises at least one waste recovery chamber and at least one air extractor, the waste recovery chamber is at least used for accommodating waste in the growth reaction chamber, and the waste recovery chamber is communicated with the reaction chamber through a discharge pipeline;
the air extractor is communicated with the waste recovery chamber through a second air guide pipeline and at least used for extracting air in the waste recovery chamber, so that a second air pressure difference is formed between the waste recovery chamber and the reaction chamber, and the second air pressure difference can drive waste in the reaction chamber to flow into the waste recovery chamber.
Further, the waste recovery chamber is a sealed chamber.
Furthermore, the feed inlet of the discharge pipeline is arranged at the bottom of the reaction chamber.
Further, the growth arrest monitoring unit comprises an X-ray growth monitoring device.
In another aspect, an embodiment of the present invention further provides a method for continuously growing a large-size high-quality nitride single crystal by a flux method, including:
providing a system for continuously growing large-size high-quality nitride single crystals by the flux method;
raw materials required for growing the nitride single crystal are filled in a reaction chamber of the reaction growth unit, and growth conditions are regulated and controlled to grow the nitride single crystal;
and monitoring the growth state of the nitride single crystal by a growth stagnation monitoring unit, and judging whether the waste material in the reaction chamber needs to be led out by a waste material recovery unit and/or the raw material required by the growth of the nitride single crystal needs to be input into the reaction chamber by a raw material supply unit according to the growth state, so that the nitride single crystal continuously grows to reach the required specification.
Further, the method for continuously growing the large-size high-quality nitride single crystal by the flux method specifically comprises the following steps: collecting intensity signals of a nitride characteristic peak in the reaction chamber by the X-ray growth monitoring device, obtaining a height difference value between the liquid level of the raw material in the reaction chamber and the epitaxial growth surface of the nitride single crystal according to the intensity signals of the nitride characteristic peak, and comparing the height difference value with a set threshold value so as to judge whether the growth of the nitride single crystal is stopped or not,
if so, leading out the waste in the reaction chamber by a waste recovery unit and/or inputting the raw materials required for growing the nitride single crystal into the reaction chamber by a raw material supply unit so as to continue growing the nitride single crystal, and if not, not starting the waste recovery unit and/or the raw material supply unit; preferably, if the growth of the nitride single crystal is stopped, the waste material in the reaction chamber is first taken out by the waste material recovery unit, and then the raw material required for growing the nitride single crystal is fed into the reaction chamber by the raw material supply unit, so that the nitride single crystal continues to grow.
Further, the method for continuously growing the large-size high-quality nitride single crystal by the flux method specifically comprises the following steps: inert gas is input into the raw material supply chamber by a gas supply device in the raw material supply unit, a first gas pressure difference is formed between the raw material supply chamber and the reaction chamber, and the raw material in the raw material supply chamber is driven to flow into the reaction chamber by the first gas pressure difference.
Further, the method for continuously growing the large-size high-quality nitride single crystal by the flux method specifically comprises the following steps: and pumping out the gas in the waste recovery chamber by using a pumping device in the waste recovery unit, forming a second air pressure difference between the waste recovery chamber and the reaction chamber, and driving the waste in the reaction chamber to flow into the waste recovery chamber by using the second air pressure difference.
Further, the method for continuously growing the large-size high-quality nitride single crystal by the flux method specifically comprises the following steps:
the method comprises the following steps of loading raw materials required for growing the nitride single crystal into a reaction chamber of a reaction growth unit, placing seed crystals into the reaction chamber, regulating and controlling growth conditions, and growing the nitride single crystal so that the raw materials for growing the nitride single crystal grow in the reaction chamber to form the nitride single crystal;
collecting intensity signals of characteristic peaks of nitrides in a reaction chamber by an X-ray growth monitoring device, judging whether the growth of the nitride single crystals is stopped or not, if the reaction is stopped and lagged, leading out residual waste materials in the reaction chamber by a waste material recovery unit, and then inputting at least one raw material required for growing the nitride single crystals into the reaction chamber by a raw material supply unit so that the liquid level of the raw material in the reaction chamber is higher than the epitaxial growth surface of the nitride single crystals, and simultaneously enabling the ratio of various raw materials in the reaction chamber to reach a preset value, so that the reaction for growing and forming the nitride single crystals is continuously carried out, and further the large-size high-quality nitride single crystals are continuously grown; further, the nitride single crystal includes a gallium nitride single crystal.
Further, the raw materials are molten raw materials.
Further, the raw material comprises metal gallium, metal sodium and carbon additive, or the raw material comprises metal aluminum, metal barium and carbon additive.
As will be described in further detail with reference to the accompanying drawings and specific examples, it should be noted that the process conditions for growing the gallium nitride single crystal by the flux method in the embodiments of the present invention can be realized by known process conditions of those skilled in the art, and are not described herein in detail, wherein the X-ray growth monitoring device, the air pumping device, the air supply device, the flow meter, the stirring device, the heating device, the rotation speed monitoring and adjusting device, and the like, which are used in the present invention, may all adopt existing known equipment, which may all be obtained commercially, and the control unit used in the present invention may be a PLC controller, and the like, wherein the adopted numerical control program, and the like, may all be obtained commercially.
Example 1
Referring to fig. 1, a system for continuously growing a large-sized high-quality nitride single crystal by a flux method includes: the device comprises a reaction growth unit, a raw material supply unit, a waste recovery unit, a growth stagnation monitoring unit and a control unit.
Specifically, the reaction growth unit includes a reaction chamber 100 in which a nitride single crystal can be reaction-grown.
Specifically, the raw material supply unit comprises a raw material supply chamber 210 and a gas supply device 250, wherein the raw material supply chamber 210 is at least used for accommodating raw materials required for growing nitride single crystals, the raw material supply chamber 210 is communicated with the reaction chamber 100 through a feeding pipeline 230, the gas supply device 250 is communicated with the raw material supply chamber 210 through a gas inlet pipeline 260 and is at least used for supplying inert gas to the raw material supply chamber 210, so that a first gas pressure difference is formed between the raw material supply chamber 210 and the reaction chamber 100, and the first gas pressure difference can drive the raw materials in the raw material supply chamber 210 to flow into the reaction chamber along the feeding pipeline 230;
specifically, the waste recycling unit includes a waste recycling chamber 310 and an air extractor 330, the waste recycling chamber 310 is at least used for accommodating the waste in the growth reaction chamber 100, the waste recycling chamber 310 is communicated with the reaction chamber 100 through a discharge pipeline 320, the air extractor 330 is communicated with the waste recycling chamber 310 through a first air extraction pipe 340 and is at least used for extracting the gas in the waste recycling chamber 310, so as to form a second air pressure difference between the waste recycling chamber 310 and the reaction chamber 100, and the second air pressure difference can drive the waste in the reaction chamber 100 to flow into the waste recycling chamber 310 along the discharge pipeline 320.
Specifically, growth arrest monitoring unit includes X ray growth monitoring devices, and X ray growth monitoring devices is used for at least right the growth state of nitride single crystal monitors, and, the control unit still with air feeder 250, air exhaust device 330, X ray growth monitoring devices connect, the control unit is used for the basis at least growth arrest monitoring units's monitoring signal regulates and control raw materials supply unit, waste recovery unit's operating condition, and the control unit mainly regulates and control the operating condition of air feeder 250, air exhaust device 330 through the operating condition of regulation control raw materials supply unit, waste recovery unit's operating condition.
Specifically, referring to fig. 2 again, the raw material replenishing chamber 210 is further provided with a stirring device 220 and a heating device, the heating device can heat the raw material to heat the raw material in the raw material replenishing chamber 210 to a growth temperature required for growing the nitride single crystal, and the stirring device 220 can make the raw material in the raw material replenishing chamber 210 more uniformly mixed and heated, thereby avoiding local supercooling; of course, the stirring device 220 and the heating device may be integrally provided, and the stirring device may also be connected with a rotation speed monitoring and adjusting device, which are both connected with the control unit.
Specifically, a flow rate meter 240 is further disposed in the feeding pipeline 230, the flow rate meter 240 is connected to the control unit and at least used for monitoring uniformity of the raw material flowing through the feeding pipeline 230 and ensuring that uniform-quality nitride single crystals are obtained, the flow rate meter 240 is connected to the flow rate display screen and can display real-time flow rate parameters, and when the raw material is not uniform, the stirring device disposed in the sealed chamber 210 is controlled to rotate to improve uniformity of the raw material and ensure uniform supply of the growth raw material.
Specifically, the control unit includes a control screen, and the operating parameters of each device can be set through the control screen.
Specifically, the feeding pipeline 230 enters from the bottom of the reaction chamber 100, the discharge port of the feeding pipeline is far away from the epitaxial surface of the nitride single crystal, the raw materials enter from the bottom of the reaction chamber 100 and are far away from the epitaxial growth surface of the nitride single crystal, so that the raw materials can be guaranteed to have enough time to be fully mixed and diffused again before reaching the epitaxial growth surface of the nitride single crystal, the problem that local saturation is too large near the epitaxial growth surface of the nitride single crystal is prevented, and the occurrence of spontaneous nucleation polycrystal phenomenon is inhibited.
Specifically, the raw material supply chamber 210 and the waste material recovery chamber 310 may be disposed in the same container and separated by a partition 400, or the raw material supply chamber 210 and the waste material recovery chamber 310 may be disposed in different sealed containers, respectively, where the raw material supply chamber 210 may be one or more, and may contain a plurality of raw materials required for growing a nitride single crystal in the same raw material supply chamber 210 according to a predetermined ratio, or may contain a plurality of raw materials required for growing a nitride single crystal in a plurality of raw material supply chambers 210 according to a predetermined ratio, and each raw material supply chamber 210 contains one raw material.
Referring to fig. 2-4, taking the growth of gallium nitride crystal by flux method as an example, the growth of gallium nitride crystal by using a system for continuously growing large-size high-quality nitride single crystal by flux method as shown in fig. 1 may specifically include the following processes:
a seed crystal for growing a gallium nitride single crystal is placed in the reaction chamber 100, and a raw material (e.g., metal gallium, metal sodium, carbon additive) for growing the gallium nitride single crystal is grown in the reaction chamber 100 under conditions of 3-10MPa and about 800 ℃ to form the gallium nitride single crystal, and the raw material for growth is consumed as the gallium nitride single crystal grows.
Specifically, the intensity signal of the gallium nitride characteristic peak in the reaction chamber is acquired by the X-ray growth monitoring device, the X-ray growth monitoring device acquires the height difference between the liquid level of the molten raw material in the reaction chamber and the epitaxial growth surface of the gallium nitride single crystal according to the intensity signal of the gallium nitride characteristic peak, and the height difference is compared with the set threshold value, so that whether the growth of the gallium nitride single crystal is stopped or not is judged.
When the growth stops, the gas pumping device 330 is used for pumping the gas in the waste material recovery chamber 310, so as to form a second gas pressure difference between the waste material recovery chamber 310 and the reaction chamber 100, so that the waste material in the reaction chamber 100 flows into the waste material recovery chamber 310 under the driving of the second gas pressure difference, then the gas supply device 250 is used for inputting an inert gas (such as argon) into the raw material supply chamber 210, so as to form a first gas pressure difference between the raw material supply chamber 210 and the reaction chamber 100, and the raw material in the raw material supply chamber 210 is driven to flow into the reaction chamber 100 by the first gas pressure difference, so as to make the liquid level of the molten raw material in the reaction chamber 100 higher than the epitaxial growth surface of the nitride single crystal, and simultaneously make the mixture ratio of a plurality of raw materials in the reaction chamber reach a preset value, so as to continuously generate the reaction for growing the nitride single crystal, thereby obtaining the large-size high-quality nitride single crystal.
Specifically, the waste materials in the reaction chamber are led out through the waste material recovery unit so as to ensure that the raw material ratio to be supplemented is not influenced by the components of the waste materials, and raw materials with a certain ratio are supplemented into the reaction chamber through the raw material supplementing unit so as to realize the consistency of the raw material ratio, so that the gallium nitride single crystal uniformly and continuously grows, and the uniformity of the quality of the gallium nitride crystal is further ensured.
Specifically, the raw material supply unit may be one or more of a plurality of raw materials for growing the gallium nitride single crystal, and the one or more raw materials may be accommodated in one raw material supply chamber according to a predetermined ratio, or a plurality of raw material supply chambers 210 may be provided, and the plurality of raw materials required for growing the nitride single crystal may be accommodated in the plurality of raw material supply chambers 210 according to a predetermined ratio, respectively.
For example, the process of performing a gallium nitride crystal using a system for continuously growing a large-size high-quality nitride single crystal by a flux method as shown in fig. 1 may include:
placing a seed crystal for growing a gallium nitride single crystal in a reaction chamber;
firstly, controlling a gas supply device to supply gas to a raw material supply chamber for containing a doped silicon raw material so as to input the doped silicon raw material into a reaction chamber to grow N-type gallium nitride;
then, collecting intensity signals of characteristic peaks of the nitride in the reaction chamber by using an X-ray growth monitoring device, and judging whether the growth of the nitride single crystal is stopped or not, if so, recovering the residual doped silicon waste from the reaction chamber to a waste recovery chamber by controlling an air extraction device to extract air;
then, inputting the raw material of the non-doped raw material contained in the other raw material supply chamber into the reaction chamber by controlling the gas supply device to supply gas to the raw material supply chamber so as to grow a non-doped layer;
similarly, after the non-doped layer grows to a certain thickness, the residual non-doped waste is recycled from the reaction chamber to the waste recycling chamber by controlling the air exhaust device to work;
then, the metal-doped Mg raw material contained in one raw material replenishment chamber is introduced into the reaction chamber by controlling the gas supply device to supply gas to the raw material replenishment chamber, so as to grow a P-type gallium nitride layer, thereby forming a PIN structure for gallium nitride epitaxy, as shown in fig. 4.
It is worth noting that after the growth of each structural layer is finished, the raw material recovery unit is used for recovering the growth raw materials with the proportion, so that when the structural layer of the next layer grows, residual raw material impurities for growing the structural layer of the previous layer exist in the reaction chamber, and the performance of the PIN structure is prevented from being influenced.
Specifically, in the reaction raw materials for growing and forming the nitride single crystal, the proportion of the metal gallium, the metal sodium and the carbon additive directly influences the growth quality of the gallium nitride single crystal, so that the maintenance of the optimal raw material proportion is very important for the growth of high-quality gallium nitride; during the reaction, the sodium metal acts as a fluxing agent and can promote N2The triple bond is broken, the solubility of nitrogen atoms in the molten mixed raw material is increased, wherein, the metal gallium and the nitrogen atoms are combined to generate the gallium nitride single crystal; in the reaction process, the sodium metal is not consumed, and the proportioning among the raw materials is separated from the initial proportioning of the reaction along with the continuous consumption of the gallium metal, so that the growth quality of the gallium nitride single crystal is uneven, and the recovery of the residual waste material is very important.
It should be noted that the present invention is not limited to the preparation of the nitride single crystal with such a structure, and those skilled in the art can also prepare different nitride device structures by increasing the number of the raw material supplement tanks, changing the raw material proportion and the kind of the doping elements, so that the preparation of the device structure can be completed by one-time furnace charging, thereby reducing the cost of the device structure preparation. The system for continuously growing the large-size high-quality nitride single crystal by the flux method provided by the embodiment of the invention has the advantages of simple structure and simplicity and convenience in operation and use, and the system provided by the embodiment of the invention is provided with the raw material supply unit for automatically and uniformly supplying raw materials, and realizes the automatic continuous and uniform growth of the gallium nitride single crystal by continuously supplying growth raw materials in the growth process.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A system for continuously growing large-size high-quality nitride single crystals by a flux method is characterized by comprising a reaction growth unit, a raw material supply unit, a waste material recovery unit, a growth stagnation monitoring unit and a control unit, wherein the control unit is respectively connected with the reaction growth unit, the raw material supply unit, the waste material recovery unit and the growth stagnation monitoring unit;
the reaction growth unit comprises a reaction chamber for reacting and growing the nitride single crystal, the raw material supply unit and the waste material recovery unit are respectively communicated with the reaction chamber, the raw material supply unit is at least used for providing raw materials required by growing the nitride single crystal for the reaction chamber, and the waste material recovery unit is at least used for guiding out waste materials in the reaction chamber;
the growth stagnation monitoring unit is at least used for monitoring the growth state of the nitride single crystal; and
the control unit is at least used for regulating and controlling the working states of the raw material supply unit and the waste recovery unit according to the monitoring signal of the growth stagnation monitoring unit.
2. The system for continuously growing a large-size high-quality nitride single crystal according to claim 1, wherein: the raw material supply unit comprises at least one raw material supply chamber and at least one gas supply device, the raw material supply chamber is at least used for containing at least one raw material required by growing nitride single crystals, and the raw material supply chamber is communicated with the reaction chamber through a feeding pipeline;
the gas supply device is communicated with the raw material supply chamber through a first gas guide pipeline and is at least used for providing inert gas for the raw material supply chamber, a first gas pressure difference is formed between the raw material supply chamber and the reaction chamber, and the raw material in the raw material supply chamber can be driven to flow into the reaction chamber by the first gas pressure difference.
3. The system for continuously growing a large-size high-quality nitride single crystal according to the flux method of claim 2, wherein: and the feeding pipeline enters the reaction chamber from the bottom of the reaction chamber, and a discharge port of the feeding pipeline is far away from the epitaxial surface of the nitride single crystal.
4. The system for continuously growing a large-size high-quality nitride single crystal according to the flux method of claim 2, wherein: the feeding pipeline is also internally provided with a flow rate meter which is at least used for monitoring the uniformity of the raw materials flowing through the feeding pipeline.
5. The system for continuously growing a large-size high-quality nitride single crystal according to the flux method of claim 2, wherein: and a stirring device is also arranged in the raw material supply chamber.
6. The system for continuously growing a large-size high-quality nitride single crystal according to the flux method of claim 5, wherein: the stirring device is also connected with a rotating speed monitoring and adjusting device, and the rotating speed monitoring and adjusting device is also connected with the control unit.
7. The system for continuously growing a large-size high-quality nitride single crystal according to claim 1, wherein: the raw material supply unit comprises a plurality of raw material supply chambers, and the raw material supply chambers are respectively used for accommodating at least one raw material required by different structural layers of the growing nitride single crystal.
8. The system for continuously growing a large-size high-quality nitride single crystal according to claim 1, wherein: the waste recovery unit comprises at least one waste recovery chamber and at least one air extractor, the waste recovery chamber is at least used for containing waste in the growth reaction chamber, and the waste recovery chamber is communicated with the reaction chamber through a discharge pipeline;
the air extractor is communicated with the waste recovery chamber through a second air guide pipeline and at least used for extracting air in the waste recovery chamber, so that a second air pressure difference is formed between the waste recovery chamber and the reaction chamber, and the second air pressure difference can drive waste in the reaction chamber to flow into the waste recovery chamber.
9. The system for continuously growing a large-size high-quality nitride single crystal according to claim 8, wherein: the feed inlet of the discharge pipeline is arranged at the bottom of the reaction chamber.
10. The system for continuously growing a large-size high-quality nitride single crystal according to claim 1, wherein: the growth arrest monitoring unit comprises an X-ray growth monitoring device.
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