CN112899783B - Method for manufacturing coralline polycrystalline gallium nitride crystal by using normal-pressure HVPE - Google Patents
Method for manufacturing coralline polycrystalline gallium nitride crystal by using normal-pressure HVPE Download PDFInfo
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Abstract
A method for manufacturing coral polycrystalline gallium nitride crystals by using normal-pressure HVPE is characterized by comprising the following steps: 1) placing seed particles with the diameter of about 1mm on a carrying disc at intervals of about 10 mm; 2) introducing nitrogen and hydrogen into the reaction zone, heating to 900-class 1000 ℃ and keeping for 10 minutes, and cleaning impurities such as moisture, oxygen and the like on the surface of the seeds; 3) controlling the temperature of the reaction zone and the growth zone at 850-900 ℃ and 950-1000 ℃ respectively by a heating furnace, and introducing ammonia gas for 10-30 minutes when the temperature is stable so as to nitride the surface of the seed; 4) introducing hydrogen chloride at the temperature of 1000-1020 ℃ in the growth area in the amount of 0.05-0.4 mol/h for 30-90 min to generate cauliflower-shaped gallium nitride; 5) when the temperature in the growth area is continuously raised to 1020-1070 ℃, hydrogen chloride gas is continuously introduced in an amount of about 0.05-0.2 mol/h, and the coral-shaped gallium nitride forming body can be obtained after the growth time is 2-100 h.
Description
Technical Field
The invention relates to a gallium nitride crystal production technology, in particular to a method for manufacturing coralline polycrystalline gallium nitride crystals by normal-pressure HVPE.
Background
The growth of gallium nitride crystals by HVPE (Hydride Vapor Phase Epitaxy) is a well-established technique used in the art for many years, and its basic principle is as follows:
1) heating the metal gallium source in the gallium boat to 850 ℃, introducing hydrogen chloride gas, and reacting to generate gallium chloride and hydrogen Hcl + Ga- - > GaCl + H2
2) Gallium chloride enters the reaction chamber to be mixed with ammonia gas to react to generate gallium nitride and hydrogen chloride, and the temperature is between 1000 ℃ and 1100 ℃, GaCl + NH3- - > GaN + Hcl
Polycrystalline gallium nitride is a raw material for a process for growing single-crystal gallium nitride by an ammonothermal method, and is required to have high purity and large coral-shaped grains. The polycrystalline gallium nitride grown by the HVPE method can meet the requirements, and has the characteristics of high growth rate, high utilization rate and the like.
For many years, many researchers and manufacturers in the world have explored this situation in order to explore and further improve the manufacturing techniques for gallium nitride crystals.
Some researchers started with a gallium boat device of polycrystalline gallium nitride grown by an HVPE method, and made certain improvements on the gallium boat device which is used in the prior art, so as to improve the purity of gallium nitride crystals; some manufacturers have started with the process of the gallium nitride crystal production technology, and desire to obtain gallium nitride crystals with more desirable purity.
Chinese patent documents: the two Chinese homologous patents CN 1993292B and CN 102282298B are patents before 2010 and older obsolete technologies. CN 1993292B is to make ammonia react with metal gallium directly, CN 102282298B is to let ammonia and hydrogen chloride pass into the reaction chamber containing metal gallium at the same time, make metal gallium react with ammonium chloride steam, the gallium nitride crystal produced by these two methods is powder, it is not suitable for using as raw material to grow gallium nitride single crystal by ammonothermal method.
JP2014-139118A also discloses "a method for producing a group 13 metal nitride polycrystal of the periodic table", proposing a process control technique for producing a group 13 metal nitride.
Although the above technical solution proposes a process flow, and in the specific embodiment, technical parameters such as temperature and pressure in the specific process are also disclosed, it is still difficult for the applicant who is also engaged in HVPE gallium nitride crystal production to implement and achieve the desired effect by those of ordinary skill in the art, and in the above disclosed production process, the hydrogen chloride gas is introduced only in 1 step, that is, after reaching a predetermined temperature, in a certain amount until the reaction is finished. This has not achieved the desired results for obtaining the desired large coral-like granular gallium nitride crystals suitable for use in the next process.
Therefore, it is expected by those skilled in the art to further explore a manufacturing technique for growing coralliform polycrystalline gallium nitride crystals by using a gallium boat and HVPE, and to explore a manufacturing technique for polycrystalline gallium nitride crystals that can be grown efficiently and have a controlled morphology.
Disclosure of Invention
The purpose of the invention is as follows: aims to provide a polycrystalline gallium nitride manufacturing technology which can grow efficiently and has controllable appearance.
The method for manufacturing the coralliform polycrystalline gallium nitride crystal by the normal-pressure HVPE comprises the following specific steps:
step 1: seed particles are placed on the carrying disc 8, the size of the seeds is about 1mm, the diameter of the seeds is about, and the interval is about 10 mm;
step 2: introducing nitrogen and hydrogen into the reaction zone B, heating to 900-;
and step 3: respectively controlling the temperature of the reaction zone B and the temperature of the growth zone C at 900 ℃ of 850-;
and 4, step 4: introducing hydrogen chloride at the temperature of 1000-1020 ℃ in the growth zone C for 30-90 minutes in an amount of 0.05-0.4 mol/h to generate cauliflower-shaped gallium nitride;
and 5: when the temperature in the growth area is continuously raised to 1020-1070 ℃, hydrogen chloride gas is continuously introduced in an amount of about 0.05-0.2 mol/h, and the coral-shaped gallium nitride forming body can be obtained after the growth time is 2-100 h.
Further, the seed is any one of gallium nitride, aluminum nitride and aluminum oxide.
Furthermore, the total input amount of the nitrogen and hydrogen introduced according to step 2 should be controlled between 1000sccm and 20000sccm, wherein the input amount of the hydrogen is 3-8% of the total input amount.
Further, when the ammonia gas is introduced in the step 3, the amount of the introduced ammonia gas is 4mol to 10mol per hour.
Compared with the prior similar process method, the method for manufacturing the coralline polycrystalline gallium nitride crystal by the normal-pressure HVPE, which is proposed according to the technical scheme, has the greatest advantages that: by controlling the temperature change and introducing hydrogen chloride gas twice, the volume and the surface area of the gallium nitride crystal are increased, and conditions are created for obtaining more useful coral-shaped gallium nitride.
Drawings
FIG. 1 is a schematic diagram of the structure and operation of a vertical atmospheric HVPE apparatus;
FIG. 2 is a photograph of a cauliflower-like gallium nitride crystal;
FIG. 3 is a photograph of coral-shaped gallium nitride crystals.
In the figure:
1-hydrogen flow control meter; 2-nitrogen flow control meter; 3-hydrogen chloride flow controller;
4-ammonia flow controller; 5-hydrogen chloride gas; 6-ammonia gas; 7-an exhaust gas outlet;
8-carrying disc; 9-substrate seed; 10-gallium chloride; 11-a carrier gas;
a-metallic gallium; b-a source region; a C-growth region; d-heating furnace.
Detailed Description
The method for preparing the coral-shaped polycrystalline gallium nitride crystal by the normal-pressure HVPE has the core idea that hydrogen chloride gas is input into a growth area twice, cauliflower-shaped gallium nitride is generated in the growth area when the hydrogen chloride gas is input for the first time, and a final product, namely coral-shaped gallium nitride is generated in the growth area after the hydrogen chloride gas is input for the second time.
The invention is further explained by combining the attached drawings of the specification, and the specific embodiment of the invention is given.
Embodiments of the present invention are further described below in conjunction with a vertical atmospheric HVPE apparatus as shown in fig. 1.
Various gases employed in the present invention: the nitrogen, the hydrogen chloride gas and the ammonia gas are respectively regulated and controlled by a flow controller provided with an inlet pipe; heating metal gallium arranged in a gallium boat in a reaction zone, wherein the heating temperature is generally 850-; introducing hydrogen chloride gas through the inlet pipe, reacting with liquid metal gallium to generate gaseous gallium chloride, and introducing the gaseous gallium chloride into the growth region through the next section of pipeline; the temperature of the growth region is controlled at 900-1100 ℃ to provide a proper crystallization temperature for the formation of gallium nitride; mixing ammonia gas and gaseous gallium chloride at the position of the carrying disc, reacting to generate gallium nitride, and depositing on the surface of the seed particles on the carrying disc; finally, various gases which are not reacted flow out of the growth area through a tail gas pipeline at the tail end of the gallium boat.
The method for manufacturing the coralliform polycrystalline gallium nitride crystal by the normal-pressure HVPE comprises the following specific steps:
step 1: seed particles are placed on the carrying disc, the size of the seeds is about 1mm, the diameter of the seeds is about, and the interval is about 10 mm.
In the actual manufacturing process, the seeds can be any one of gallium nitride, aluminum nitride and aluminum oxide, meanwhile, special description is needed, seed particles can not be placed, and gallium nitride particles formed on the carrying disc can be used as the seed particles through early-stage reaction; practice has shown that the latter method is used: due to the time taken for the pre-reaction and the consumption of raw material, it is less efficient than placing the seed particles directly.
Step 2: introducing nitrogen and hydrogen into the reaction cavity, wherein the hydrogen accounts for 3-8% of the total flow, the total flow of the inlet gas is set to be 1000-20000 sccm, and the nitrogen and the hydrogen are used for cleaning the moisture and the oxide impurities in the source region and the reaction region and on the surface of the seed when the temperature of the source region and the growth region begins to gradually rise to 900-1100 ℃ and is kept for 10-30 minutes after the temperature reaches the set value.
And step 3: when the temperature of the growth area reaches 950-1000 ℃, the temperature of the source area reaches 850-900 ℃, ammonia gas starts to be introduced, when the temperatures of the two reaction areas reach stability, the ammonia gas starts to be introduced, the reaction is kept for 10-30 minutes, and the ammonia gas introduction control amount is 4-10 mol/h; for nitriding the surface of the seed;
and 4, step 4: after the temperature is continuously heated, when the temperature of the growth area C reaches 1000-1020 ℃, introducing hydrogen chloride in an amount of 0.05-0.4 mol/h for 30-90 minutes to generate cauliflower-shaped gallium nitride shown in the attached figure 1 in the growth area C;
in the process of the step, gallium nitride crystals with different directions begin to grow on the surface of the seed, and the volume and the surface area begin to gradually increase; however, due to the relationship of temperature and other conditions, the gallium nitride generated at this time is in a cauliflower shape, and the purpose of this step is to create conditions for the subsequent growth of coral-shaped gallium nitride.
The step 4 is a key step of the whole manufacturing process, more polycrystalline growth points can be formed along with the expansion of the surface area, the efficiency is improved, and the subsequent crystal growth direction is easy to control.
And 5: the temperature of the growth area is continuously increased to 1020-1070 ℃, hydrogen chloride gas is continuously introduced again in the amount of about 0.05-0.2 mol/h, and the coral-shaped gallium nitride forming body shown in the figure 2 can be obtained after the growth time is 2-100 h.
The above are only specific embodiments of the present invention according to the technical solutions provided by the applicant, and any modifications that are not essential to the technical solutions provided by the ordinary skilled person in the art should be considered as falling within the protection scope of the present invention.
Claims (4)
1. A method for manufacturing coral polycrystalline gallium nitride crystals by using normal-pressure HVPE comprises the following specific steps:
step 1: placing seed particles on the carrying disc 8, wherein the size of the seeds is 1mm, the diameter of the seeds is 1mm, and the interval is 10 mm;
and 2, step: heating metal gallium arranged in a gallium boat in a reaction zone, wherein the heating temperature is generally 850-;
introducing nitrogen and hydrogen into the reaction zone B, heating to 900-1000 ℃ and keeping for 10 minutes to clean water and oxygen impurities in the reaction zone B and on the surface of the seeds;
and step 3: respectively controlling the temperature of the reaction zone B and the temperature of the growth zone C at 900 ℃ of 850-;
and 4, step 4: introducing hydrogen chloride at the temperature of 1000-1020 ℃ in the growth region C for 30-90 minutes in an amount of 0.05-0.4 mol/hour to generate cauliflower-shaped gallium nitride; introducing hydrogen chloride gas through the inlet pipe, reacting with liquid metal gallium to generate gaseous gallium chloride, and introducing the gaseous gallium chloride into the growth region through the next section of pipeline;
and 5: when the temperature in the growth area is continuously raised to 1020-1070 ℃, hydrogen chloride gas is continuously introduced in an amount of 0.05-0.2 mol/h, and the coral-shaped gallium nitride forming body can be obtained after the growth time is 2-100 h.
2. The method of making a coral-shaped polycrystalline gallium nitride crystal by atmospheric pressure HVPE of claim 1, wherein: the seed is any one of gallium nitride, aluminum nitride and aluminum oxide.
3. The method of claim 1, wherein the atmospheric pressure HVPE produces coral-shaped polycrystalline gallium nitride crystals, and wherein: the total input amount of the nitrogen and the hydrogen introduced in the step 2 is controlled to be between 1000sccm and 20000sccm, wherein the input amount of the hydrogen accounts for 3 to 8 percent of the total input amount.
4. The method of claim 1, wherein the atmospheric pressure HVPE produces coral-shaped polycrystalline gallium nitride crystals, and wherein: when the ammonia gas is introduced in the step 3, the introduction amount of the ammonia gas is 4-10 mol/h.
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