Patent Grant
11795573
This application claims a priority of Japanese Patent Application No. 2020-115825 filed on Jul. 3, 2020, the contents of which is incorporated herein by reference.
The technical field relates to a method of manufacturing a group III nitride crystal.
Group III nitride crystals of GaN etc. are expected to be applied to next-generation optical devices such as high-output LEDs (light emitting diodes) and LDs (laser diodes), and next-generation electronic devices such as high-output power transistors mounted on EVs (electric vehicles) and PHVs (plug-In hybrid vehicles). An Oxide Vapor Phase Epitaxy (OVPE) method using a group III oxide as a raw material is used as a method of manufacturing a group III nitride crystal, as shown in WO 2015/053341.
An example of a reaction system in the OVPE method is as follows. Ga is heated, and H2O gas is Introduced in this state. The introduced H2O gas reacts with Ga to generate Ga2O gas (Formula (I)). NH gas is introduced and reacted with the generated Ga2O gas to generate a GaN crystal on a seed substrate (formula (II)).
2Ga(I)+H2O(g)→Ga2O(g)+H2(g) (I)
Ga2O(g)+2NH3(g)→2GaN(s)+H2O(g)+2H2(g) (II)
However, in the manufacturing method described in WO 2015/053341, when a group III nitride crystal is grown, a droplet of a group III metal element is generated, which causes polycrystallization in which a surface different from a growth surface is oriented by using the droplet as a starting point, and this makes it difficult to uniformly produce a high-quality crystal in the growth surface. Addition of H2O gas has been proposed for suppressing the droplet of the group III metal element; however, although the polycrystallization is suppressed by the addition of H2O gas, the H2O gas etches GaN and therefore poses a problem that a growth rate tends to decrease.
The present disclosure was conceived in view of the situations and it Is therefore one non-limiting and exemplary embodiment provides a method of manufacturing a group III nitride crystal suppressing polycrystallization and achieving a high growth rate.
In one general aspect, the techniques disclosed here feature: a method of manufacturing a group III nitride crystal according to a first aspect includes: preparing a seed substrate;
generating a group III element oxide gas;
supplying the group III element oxide gas;
supplying a nitrogen element-containing gas;
supplying an oxidizing gas containing nitrogen element containing at least one selected from the group consisting of NO gas, NO2 gas, N2O gas, and N2O4 gas; and
growing the group III nitride crystal on the seed substrate.
According to the method of manufacturing a group III nitride crystal of the present disclosure, the polycrystallization is suppressed, and a group III nitride crystal can be manufactured at a high growth rate.
Additional benefits and advantages of the disclosed embodiments will be apparent from the specification and figures. The benefits and/or advantages may be individually provided by the various embodiments and features of the specification and drawings disclosure, and need not all be provided in order to obtain one or more of the same.
The present disclosure will become readily understood from the following description of non-limiting and exemplary embodiments thereof made with reference to the accompanying drawings, in which like parts are designated by like reference numeral and in which:
<Overview of Method of Manufacturing Group III Nitride Crystal>
A method of manufacturing a group III nitride crystal according to a first aspect includes:
preparing a seed substrate;
generating a group III element oxide gas;
supplying the group III element oxide gas;
supplying a nitrogen element-containing gas;
supplying an oxidizing gas containing nitrogen element containing at least one selected from the group consisting of NO gas, NO2 gas, N2O gas, and N2O4 gas; and
growing the group III nitride crystal on the seed substrate.
In the method of manufacturing a group III nitride crystal of the present disclosure, the oxidizing gas containing nitrogen element is supplied, so that even if a group III element droplet is generated in a crystal growth process, the oxidizing gas containing nitrogen element can be reacted with the group III element droplet. Therefore, the polycrystallization of the group III nitride crystal can be prevented. Therefore, the group III nitride crystal having excellent quality can be obtained. Additionally, since the oxidizing gas containing nitrogen element is unlikely to cause an etching reaction with the formed group III nitride crystal, the growth rate of the group III nitride crystal can be increased.
Further, as a method of manufacturing a group III nitride crystal according to a second aspect, in the first aspect, further may include:
reacting the oxidizing gas containing nitrogen element with a group III element droplet.
Further, as a method of manufacturing a group III nitride crystal according to a third aspect, in the first aspect, the oxidizing gas containing nitrogen element may be supplied at a partial pressure of 7.00×10−4 atm or more and 1.75×10−3 atm or less.
Further, as a method of manufacturing a group III nitride crystal according to a fourth aspect, in the first aspect, the oxidizing gas containing nitrogen element may be supplied at a partial pressure of 7.60×10−4 atm or more and 1.30×10−3 atm or less.
Further, as a method of manufacturing a group III nitride crystal according to a fifth aspect, in the first aspect, the oxidizing gas containing nitrogen element may be supplied before the seed substrate reaches a substrate maximum achieving temperature.
Further, as a method of manufacturing a group III nitride crystal according to a sixth aspect, in the first aspect, the oxidizing gas containing nitrogen element may be supplied before the seed substrate reaches the substrate temperature of 1050° C.
Hereinafter, a manufacturing method and a manufacturing apparatus of a group III nitride crystal according to embodiments will be described with reference to the accompanying drawings. In the drawings, substantially the same members are denoted by the same reference numerals.
An overview of the method of manufacturing a group III nitride crystal according to a first embodiment of the present disclosure will be described with reference to a flowchart of
(a) At the reactive gas supply step, a reactive gas is supplied to a raw material reaction chamber (S01).
(b) At the group III element oxide gas generation step, a starting group III element source is reacted with a reactive gas (a reducing gas when the starting group III element source is an oxide, or an oxidizing gas when the starting group III element source is a metal) to generate a group III element oxide gas (S02).
(c) At the group II element oxide gas supply step, the group III element oxide gas manufactured at the group III element oxide gas generation step is supplied to a growth chamber (S03).
(d) At the nitrogen element-containing gas supply step, a nitrogen element-containing gas is supplied to the growth chamber (S04).
(e) At the oxidizing gas containing nitrogen element supply step, an oxidizing gas containing nitrogen element is supplied to the growth chamber (S05).
(f) At the group III nitride crystal generation step, the group III element oxide gas supplied into the growth chamber at the group III element oxide gas supply step is reacted with the nitrogen element-containing gas supplied into the growth chamber at the nitrogen element-containing gas supply step to manufacture a group III nitride crystal (S06).
(g) At the oxidizing gas containing nitrogen element reaction step, a group III metal droplet generated on the group III nitride crystal is reacted with the oxidizing gas containing nitrogen element supplied at the oxidizing gas containing nitrogen element supply step.
(h) At the residual gas discharge step, an unreacted gas not contributing to the generation of the group III nitride crystal is discharged out of the chamber (S08).
Through the steps described above, the group III nitride crystal can be generated on a seed substrate.
<Overview of Manufacturing Apparatus of Group III Nitride Crystal>
An overview of a group III nitride crystal manufacturing apparatus according to the first embodiment of the present disclosure will be described with reference to a schematic showing a configuration of a group III nitride crystal manufacturing apparatus 150 of
In the group III nitride crystal manufacturing apparatus 150 according to the first embodiment, a raw material reaction chamber 101 is disposed in a raw material chamber 100, and a raw material boat 104 with a starting group III element source 105 placed therein is disposed in the raw material reaction chamber 101. A reactive gas supply pipe 103 supplying a reactive gas reactive with the starting group III element source 105 is connected to the raw material reaction chamber 101. The raw material reaction chamber 101 has a group III element oxide gas discharge port 107. The reactive gas is a reducing gas when the starting group III element source 105 is an oxide or an oxidizing gas when the starting group III source 105 is a metal. The raw material chamber 100 is provided with a first carrier gas supply port 102, and the group III element oxide gas and a carrier gas supplied from the first carrier gas supply port 102 flow from a group III element oxide gas and carrier gas discharge port 108 through a connection pipe 109 into a growth chamber 111. The growth chamber 111 has a group III element oxide gas and carrier gas supply port 118, an oxidizing gas containing nitrogen element supply port 112, a nitrogen element-containing gas supply port 113, a second carrier gas supply port 114, and an exhaust port 119 and includes a substrate susceptor 117 on which a seed substrate 116 is disposed.
<Details of Manufacturing Method and Manufacturing Apparatus of Group III Nitride Crystal>
Details of a method of manufacturing a group II nitride crystal according to the first embodiment will be described. In the description of the first embodiment, a metal Ga is used as the starting group III element source 105.
(1) At the reactive gas supply step, the reactive gas is supplied from the reactive gas supply pipe 103 to the raw material reaction chamber 101.
(2) At the group III element oxide gas generation step, the reactive gas supplied to the raw material reaction chamber 101 at the reactive gas supply step reacts with the metal Ga serving as the starting group III element source 105 to generate a Ga2O gas that is the group III element oxide gas. The generated Ga2O gas is discharged from the raw material reaction chamber 101 through the group III element oxide gas discharge port 107 to the raw material chamber 100. The discharged Ga2O gas is mixed with a first carrier gas supplied from the first carrier gas supply port 102 to the raw material chamber and is supplied to the group III element oxide gas and carrier gas discharge port 108. At this step, for example, the temperature of the raw material chamber 100 heated by a first heater 106 may be set equal to or greater than 800° C., which is higher than the boiling point of the Ga2O gas, and less than 1800° C. so that the temperature is made lower than the growing chamber 111 heated by a second heater 115. The starting group III element source 105 is placed in the raw material boat 104. The raw material boat 104 may have a shape capable of increasing a contact area between the reactive gas and the starting group III element source 105.
Methods of generating the group III element oxide gas are roughly classified into a method of reducing the starting group ill element source 105 and a method of oxidizing the starting Ga source 105. For example, in the reducing method, an oxide (e.g., Ga2O3) is used as the starting group III element source 105, and a reducing gas (e.g., H2 gas, CO gas, CH4 gas, C2H6 gas, H2S gas, SO2 gas) is used as the reactive gas. On the other hand, in the oxidizing method, a non-oxide (e.g., liquid Ga) is used as the starting group III element source 105, and an oxidizing gas (e.g., H2O gas, O2 gas, CO gas, NO gas, N2O gas, NO2 gas, N2O4 gas) is used as the reactive gas. In addition to the Ga source, an in source and an Al source may be used as the starting group III element source 105. The first carrier gas may be an inert gas, H2 gas, etc.
(3) At the group III element oxide gas supply step, the Ga2O gas generated at the group III element oxide gas generation step is supplied through the group III element oxide gas and carrier gas discharge part 108, the connection pipe 109, and the group III element oxide gas and carrier gas supply port 118 to the growth chamber 111. When the temperature of the connection pipe 109 connecting the raw material chamber 100 and the growth chamber 111 is lower than the temperature of the raw material chamber 100, a reverse reaction of the reaction for generating the group III element oxide gas may occur, and the starting group III element source 105 may precipitate inside the connection pipe 109. Therefore, the connection pipe 109 may be heated by a third heater 110 so as to prevent the temperature from becoming lower than the temperature of the raw material chamber 100.
(4) At the nitrogen element-containing gas supply step, the nitrogen element-containing gas is supplied from the nitrogen element-containing gas supply port 113 to the growth chamber 111. Examples of the nitrogen element-containing gas include NH3 gas, NO gas, NO2 gas, N2O4 gas, N2H2 gas, and N2H4 gas.
(5) At the oxidizing gas containing nitrogen element supply step, the oxidizing gas containing nitrogen element is supplied from the oxidizing gas containing nitrogen element supply port 112 to the growth chamber 111. By supplying the oxidizing gas containing nitrogen element, as described later, a group ill element droplet can be reacted with the oxidizing gas containing nitrogen element to remove the group III element droplet. The oxidizing gas containing nitrogen element includes at least one selected from the group consisting of NO gas, NO2 gas, N2O gas, and N2O4 gas.
(6) At the group III nitride crystal generation step, the raw material gases supplied through the supply steps into the growth chamber 111 are combined to manufacture a group III nitride crystal. The growth chamber 111 is heated by the second heater 115 to a temperature at which the group III element oxide gas reacts with the nitrogen element-containing gas. In this case, to prevent the reverse reaction of the reaction for generating the group III element oxide gas from occurring, the growth chamber 111 may be heated so that the temperature of the growth chamber 111 does not become lower than the temperature of the raw material chamber 100 and the temperature of the connecting pipe 109. The temperature of the growth chamber 111 heated by the second heater 115 is, for example, 1000° C. or higher and 1800° C. or lower.
(7) By mixing the group III element oxide gas supplied to the growth chamber 111 through the group III element oxide gas supply step and the nitrogen element-containing gas supplied to the growth chamber 111 through the nitrogen element-containing gas supply step upstream of the seed substrate 116, the group III nitride crystal can be grown on the seed substrate 116.
<Suppression of Polycrystallization of Group III Nitride Crystal>
The quality of the group III nitride crystal can be improved by suppressing the polycrystallization of the group III nitride crystal to be grown. Causes of generation of polycrystals include generation of group II element droplets caused by decomposition of a group III nitride crystal. To suppress the polycrystallization, a method of adding an oxidizing gas (e.g., H2O gas) and reacting the oxidizing gas with a group III element droplet to remove the group III element droplet may be used. However, the oxidizing gas may etch the generated group III nitride crystal. On the other hand, in this disclosure, the oxidizing gas containing nitrogen element is used, so that an etching reaction of the group III nitride crystal hardly occurs. Therefore, the growth rate of the group III nitride crystal can be prevented from decreasing due to etching, and the growth rate of the group III nitride crystal can be increased.
For example, when the group III nitride crystal is gallium nitride and H2O gas is used as the oxidizing gas, a decomposition reaction is represented by Formula (III), and a group III element droplet removal reaction is represented by Formula (IV). The etching reaction is represented by the reverse reaction of the GaN generation reaction represented by Formula (II) described above.
2GaN(I)→Ga(g)+½N2(g) (III)
2Ga(g)+H2O(g)→Ga2O(g)+H2(g) (IV)
On the other hand, for example, when N2O gas is used as the oxidizing gas containing nitrogen element, the removal reaction of the group III element droplet can be represented by Formula (V), and the etching reaction as represented by the reverse reaction of Formula (II) does not occurs.
2Ga(g)+N2O(g)→Ga2O(g)+N2(g) (V)
The oxidizing gas containing nitrogen element may be supplied before the seed substrate 116 reaches a substrate maximum achieving temperature. In this case, the thermal decomposition of the group III nitride crystal grown on the seed substrate 116 can be suppressed.
<Suppression of Polycrystallization by Supplying Oxidizing Gas Containing Nitrogen Element>
As shown in
The oxidizing gas containing nitrogen element may be supplied at a partial pressure of 7.00×10−4 atm or more and 1.75×10−3 atm or less. In this case, the generation of the group III element droplets from the group ill nitride crystal growing on the seed substrate 116 can further be suppressed. For example, when gallium nitride is grown as the group ill nitride crystal, the generation of the Ga droplets can particularly be suppressed. The oxidizing gas containing nitrogen element may be supplied at a partial pressure of 7.60×10−4 atm or more and 1.30×10−3 atm or less.
To prevent the nitrogen element-containing gas from being decomposed due to heat from the growth chamber 111, outer walls of the nitrogen element-containing gas supply port 113 and the growth chamber 111 may be covered with a heat insulating material.
Parasitic growth of the group III nitride crystal onto a furnace wall of the growth chamber 111 and the substrate susceptor 117 may pose a problem. Therefore, the concentrations of the group III element oxide gas and the nitrogen element-containing gas can be controlled by the second carrier gas supplied from the second carrier gas supply port 114 to the growing chamber 111 to suppress the parasitic growth of the group III nitride crystal onto the furnace wall of the growth chamber 111 and the substrate susceptor 117.
Examples of the seed substrate 116 include gallium nitride, gallium arsenide, silicon, sapphire, silicon carbide, zinc oxide, gallium oxide, and ScAlMgO4.
An inert gas, H2 gas, etc. are usable as the second carrier gas.
The oxidizing gas containing nitrogen element may be supplied so that the gas can easily reach the seed substrate 116. Specifically, in the case of a vertical growth chamber shown in
The unreacted group III element oxide gas, nitrogen element-containing gas, oxidizing gas containing nitrogen element, first carrier gas, and second carrier gas are discharged from the exhaust port 119.
Group III nitride crystals of Examples 1 and 2 and Comparative Examples 1 to 3 were grown by using the growth furnace shown in
A proportion of a polycrystalline region was calculated for the obtained group III nitride crystals of Examples 1 and 2 and Comparative Examples 1 to 3. The proportion of the polycrystalline region was calculated from a proportion of an area of generated polycrystals by observing a grown crystal surface with an electron microscope. The formula used for the calculation is described as Formula (VI). The observed region is the entire growth surface grown on the seed substrate.
(area of region where polycrystals are generated)/(area of entire observed region)×100[%] (VI)
For the growth conditions, the substrate temperature was 1200° C. and the raw material temperature was 1100° C. The Ga2O gas partial pressure was 9.36×10−4 atm, the H2O gas partial pressure was 5.95×10−4 atm, the NH3 gas partial pressure was 5.25×10−2 atm, the H2 gas partial pressure was 3.33×10−1 atm, the N2 gas partial pressure was 6.13×10−1 atm, and the added N2O gas partial pressure was 8.75×10−4 atm. In Example 1, the H2O gas and the N2O gas were not supplied in a temperature raising process.
The proportion of the polycrystalline region on the GaN growth surface obtained in Example 1 was less than 0.1%, and the growth rate was 122 μm/h.
For the growth conditions, the substrate temperature was 1200° C. and the raw material temperature was 1100° C. The Ga2O gas partial pressure was 9.55×10−4 atm, the H2O gas partial pressure was 5.75×10−4 atm, the NH3 gas partial pressure was 5.25×10−2 atm, the H2 gas partial pressure was 3.32×10 atm, the N2 gas partial pressure was 6.12×10−1 atm, and the added N2O gas partial pressure was 1.75×10−3 atm. In Example 2, the H2O gas and the N2O gas were not supplied in the temperature raising process.
The proportion of the polycrystalline region on the GaN growth surface obtained in Example 2 was less than 0.5%, and the growth rate was 123 μm/h.
For the growth conditions, the substrate temperature was 1200° C. and the raw material temperature was 1100° C. The Ga2O gas partial pressure is 9.28×10−4 atm, the H2O gas partial pressure is 6.04×10−4 atm, the NH gas partial pressure was 5.26×10−2 atm, the H2 gas partial pressure was 3.33×10−1 atm, and the N2 gas partial pressure was 6.13×10−1 atm. In Comparative Example 1, none of the H2O gas nor the N2O gas was supplied in the temperature raising process.
The proportion of the polycrystalline region on the GaN growth surface obtained in Comparative Example 1 was 2.1%, and the growth rate was 124 μm/h.
For the growth conditions, the substrate temperature was 1200° C. and the raw material temperature was 1100 SC. The Ga2O gas partial pressure is 9.92×10−4 atm, the H2O gas partial pressure is 5.39×10−4 atm, the NH2 gas partial pressure was 5.25×10−2 atm, the H2 gas partial pressure was 3.33×10−1 atm, the N2 gas partial pressure was 6.13×10−1 atm, and the added H2O gas partial pressure was 8.75×10−4 atm. In Comparative Example 2, the H2O gas and the N2O gas were not supplied in the temperature raising process.
The proportion of the polycrystalline region on the GaN growth surface obtained in Comparative Example 2 was 1.4%, and the growth rate was 130 μm/h.
For the growth conditions, the substrate temperature was 1200° C. and the raw material temperature was 1100° C. The Ga2O gas partial pressure is 9.22×10−4 atm, the H2O gas partial pressure is 6.09×10−4 atm, the NH3 gas partial pressure was 5.25×10−2 atm, the H2 gas partial pressure was 3.32×10−1 atm, the N2 gas partial pressure was 6.12×10−1 atm, and the added H2O gas partial pressure was 1.31×10−3 atm. In Comparative Example 3, the H2O gas and the N2O gas were not supplied in the temperature raising process.
The proportion of the polycrystalline region on the GaN growth surface obtained in Comparative Example 3 was less than 0.1%, and the growth rate was 109 μm/h.
As can be seen from
From the above, considering the results of the growth rate and the proportion of the polycrystalline region together, it can be seen that when N2O gas is added, the generation of polycrystals can be suppressed without reducing the growth rate as compared to when H2O gas is added. When a wafer is used for device fabrication, a region of generation of polycrystals cannot drive the device due to a disordered crystal structure. Therefore, the region of generation of polycrystals can be considered as a region that cannot be used for device fabrication. Therefore, polycrystallization is suppressed by adding N2O gas, so that a high-quality group III nitride crystal can be obtained, and the group III nitride crystal can efficiently be manufactured.
an experiment was conducted by using the growth furnace shown in
The surfaces of the GaN substrates of Example 3 and Comparative Example 4 were observed with a differential interference microscope, and the number of generated polycrystals per unit area was calculated and used as a polycrystal density.
For the temperature raising conditions, heating was performed to the substrate temperature of 1200° C. and the raw material temperature of 1100° C. The added N2O gas was supplied after the substrate temperature reached 1000° C. When the added N2O gas was supplied, the partial pressures of the gases were set to the NH3 gas partial pressure of 9.08×10−1 atm, the N2 gas partial pressure of 9.08×10−2 atm, and the added N2O gas partial pressure of 9.08×10−4 atm. When the substrate temperature was less than 1000° C., the partial pressures of the gases were set to the NH3 gas partial pressure of 9.09×10−3 atm and the N2 gas partial pressure of 9.09×10−2 atm. Subsequently, the NH3 gas partial pressure was set to 0.77 atm, the N2 gas partial pressure was set to 0.23 atm, and after the substrate temperature was reduced to 500° C., the substrate temperature was reduced to room temperature in an N2 atmosphere. After the temperature rise and fall of the GaN substrate of Example 3, the polycrystalline density was 172 pieces/mm2.
For the temperature raising conditions, heating was performed to the substrate temperature of 1200° C. and the raw material temperature of 1100° C. In Comparative Example 4, N2O gas was not added. The partial pressures of the gases were set to the NH3 gas partial pressure of 9.09×10′1 atm and the N2 gas partial pressure of 9.09×10−2 atm.
As a result of the temperature rise and fall of the GaN substrate of Comparative Example 4, the polycrystalline density was 1437 pieces/mm2.
From the results of Example 3 and Comparative Example 4, it was confirmed that by adding N2O gas, the Ga droplets generated from the GaN substrate were favorably removed and polycrystallization was suppressed.
The present disclosure includes appropriately combining any embodiments and/or examples out of the various embodiments and/or examples described above, and the effects of the respective embodiments and/or examples can be produced.
According to the method of manufacturing a group III nitride crystal according to the present invention, polycrystallization can be suppressed, and the group III nitride crystal can be manufactured at a high growth rate, by supplying an oxidizing gas containing nitrogen element.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-115825 | Jul 2020 | JP | national |
| Number | Name | Date | Kind |
|---|---|---|---|
| 20020037599 | Ishida | Mar 2002 | A1 |
| 20120295418 | Melnik | Nov 2012 | A1 |
| 20160268129 | Mori | Sep 2016 | A1 |
| Number | Date | Country |
|---|---|---|
| 2015053341 | Apr 2015 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20220002904 A1 | Jan 2022 | US |
