JP2012101961A - METHOD FOR MANUFACTURING In-CONTAINING p-NITRIDE COMPOUND SEMICONDUCTOR CRYSTAL - Google Patents

Abstract

A p-type electrical characteristic is more easily obtained from a nitride compound semiconductor crystal containing In.
First, a substrate 101 is heated. Next, at least an In material, ammonia, a Group V material other than nitrogen, and a p-type dopant material are supplied onto the substrate 101. However, the V group other than nitrogen is selected from As, P, and Sb. In addition to the In material, a Ga material, an Al material, or the like may be added. Thereby, the p-type nitride compound semiconductor crystal layer 102 containing In can be formed on the substrate 101.
[Selection] Figure 1

Description

  The present invention relates to a method for producing a p-type nitride compound semiconductor crystal containing In used for a light emitting diode, a solar cell, a diode, a transistor, or the like.

  Nitride compound semiconductors composed of InN, GaN, AlN, or mixed crystals of these materials are used as materials for high-voltage transistors used in blue lasers, light-emitting elements such as light-emitting diodes, and mobile phone base stations. Is progressing. Recently, research and development aimed at application to green lasers, ultraviolet lasers, and solar cells has been actively promoted.

  Conventionally, metal-organic vapor phase epitaxy (MOCVD) and molecular beam epitaxy (MBE) have been used to grow these nitride compound semiconductor crystals, which are generally advantageous for mass production and cost reduction. The MOCVD method is often used.

In the MOCVD method, a substrate made of silicon, sapphire, SiC, or GaN is loaded on a susceptor serving as a sample stage, and an organic metal containing ammonia (NH ₃ ) and a group III element is added while the susceptor temperature is increased by a heater. Sequentially supplied onto the substrate. At this time, ammonia is thermally decomposed to generate nitrogen, and the organic metal is thermally decomposed to generate group III atoms, whereby a nitride compound semiconductor crystal grows on the substrate.

As the organic metal, trimethylindium (TMI) is used as a raw material for In, trimethylgallium (TMG) or triethylgallium (TEG) is used as a raw material for Ga, and trimethylaluminum (TMA) is used as a raw material for Al. Further, when growing a nitride compound semiconductor crystal having p-type electrical characteristics, biscyclopentadienylmagnesium (Cp ₂ Mg) is simultaneously supplied to perform doping of Mg to have n-type electrical characteristics. In the growth of a nitride compound semiconductor crystal, disilane (Si ₂ H ₆ ) or silane (SiH ₄ ) is simultaneously supplied to perform Si doping in many cases. The growth pressure is generally in the range of 9806.65 to 98066.5 Pa.

Supervised by Masashi Yamaguchi, “Development and application of high-efficiency solar cells”, CMC Publishing Co., Ltd., 2009. M. Mesrine, et al., "Efficiency of NH3 as nitrogen source for GaN molecular beam epitaxy", Appl. Phys. Lett., Vol.72, no.3, pp.350-352, 1998. A. Yamamoto, et al., "Improved Electrical Properties for Metalorganic Vapor Phase Epitaxial InN Films", phys.stat.sol. (B), vol.194, no.2, pp.510-514, 2002. AGExcimer et al., "Growth and Characterization of Epitaxial InN films on Sapphire Substrate using an ArF Excimer Laser-Assisted Metalorganic Vapor-Phase Epitaxy (La-MOVPE)", Jpn. J. Phys., Vol.42, pp.7284 -7289, 2003. http://jstshingi.jp/abst/p/09/918/fukui7.pdf Gerald B. Stringfellow, "Organometallic Vapor-Phase Epitaxy Theory ond Practce", ACADEMIC PRESS, 1999.

  By the way, the optimum growth temperature when growing a nitride compound semiconductor crystal of InN, GaN, and AlN is different. This is because the thermal stability (evaporation rate) differs depending on the material. The thermal stability has a relationship of InN <GaN <AlN. The maximum growth temperature of AlN is 1700 ° C., and the maximum growth temperature of GaN is around 1100 ° C.

  On the other hand, in a mixed crystal containing InN or InN (hereinafter referred to as a nitride compound semiconductor containing In), the thermal stability is low, so the growth temperature needs to be around 600 ° C. or less (non-patent document) 1). On the other hand, a very high temperature is required for the thermal decomposition of ammonia, which is a raw material of nitrogen, and the decomposition efficiency is about 3% even at around 600 ° C. (see Non-Patent Document 2).

  As described above, when a nitride compound semiconductor containing In is grown in a temperature range of 600 ° C. or less that can secure this thermal stability, the crystal is in a state of lack of nitrogen due to insufficient decomposition of ammonia. It is shown that. In addition, when the growth is performed at a high temperature in order to promote the decomposition of ammonia, the thermal stability of the crystal is deteriorated, and the nitrogen is easily evaporated from the crystal. In other words, in this case, the growth of the nitride compound semiconductor containing In always tends to cause a shortage of nitrogen, and a large number of nitrogen vacancy defects are generated in the grown crystal. The nitrogen vacancies generated in the nitride compound semiconductor containing In are known to work as donors (see Non-Patent Document 3), and the electrical characteristics in the undoped state are made n-type.

  Thus, in a nitride compound semiconductor containing In, which is likely to be in an n-doped undoped state, p-type electrical characteristics are obtained due to the n-type background carrier even if Mg is generally doped as a p-type dopant. There is a problem that it is difficult to obtain.

  Here, in order to reduce the vacancy density of nitrogen in the nitride compound semiconductor containing In, a method of accelerating the decomposition of ammonia by irradiating ArF excimer laser (see Non-Patent Document 4), ammonia using a Pt catalyst A method (see Non-Patent Document 5) for promoting the decomposition of benzene has been proposed. However, none of the techniques has yet reached the control of p-type electrical characteristics.

  The present invention has been made to solve the above-described problems, and it is an object of the present invention to more easily obtain p-type electrical characteristics in a nitride compound semiconductor crystal containing In. To do.

  A method for producing a p-type nitride compound semiconductor crystal containing In according to the present invention comprises a step of heating a substrate, and at least a group V material other than an In material, ammonia, nitrogen, and a p-type dopant material on the substrate. And the group V is selected from As, P, and Sb.

  In the method for producing a p-type nitride compound semiconductor crystal containing In, the p-type dopant may be Mg.

  The method for producing a p-type nitride compound semiconductor crystal containing In includes, for example, forming a p-type nitride compound semiconductor crystal containing In selected from InN, InGaN, InAlN, and InAlGaN on a substrate. .

  In the method for producing a p-type nitride compound semiconductor crystal containing In, the substrate may be made of a material selected from silicon, sapphire, SiC, and GaN.

  As described above, according to the present invention, since a Group V raw material other than nitrogen is also added, the nitride compound semiconductor crystal containing In can easily obtain p-type electrical characteristics. Effect.

FIG. 1 is a flowchart for explaining a method of manufacturing a p-type nitride compound semiconductor crystal containing In according to an embodiment of the present invention. FIG. 2 is a characteristic diagram showing thermal decomposition characteristics of arsine, phosphine and trimethylantimony. FIG. 3 is a sequence diagram showing a sequence related to a change in substrate temperature and supply of each source gas when arsine is used in the embodiment of the present invention. FIG. 4 is a sequence diagram showing a sequence relating to a change in substrate temperature and supply of each source gas when phosphine is used in the embodiment of the present invention. FIG. 5 is a sequence diagram showing a sequence relating to a change in substrate temperature and supply of each source gas when trimethylantimony is used in the embodiment of the present invention. FIG. 6 is a sequence diagram showing a sequence related to the change in substrate temperature and the supply of each source gas when the sapphire substrate in the embodiment of the present invention is used. FIG. 7 is a sequence diagram showing a sequence related to the change in substrate temperature and the supply of each source gas when the SiC substrate in the embodiment of the present invention is used. FIG. 8 is a sequence diagram showing a sequence relating to a change in substrate temperature and supply of each source gas when a GaN substrate is used in the embodiment of the present invention.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a flowchart for explaining a method of manufacturing a p-type nitride compound semiconductor crystal containing In according to an embodiment of the present invention.

  In this manufacturing method, first, as shown in FIG. 1A, the substrate 101 is heated (step S101). Next, at least an In material, ammonia, a Group V material other than nitrogen, and a p-type dopant material are supplied onto the substrate 101 (step S102). However, the V group other than nitrogen is selected from As, P, and Sb. In addition to the In material, a Ga material, an Al material, or the like may be added. Thereby, a p-type nitride compound semiconductor crystal layer 102 containing In can be formed on the substrate 101 as shown in FIG.

  As described above, a V group material selected from As, P, and Sb is supplied together with an In material and ammonia to fill nitrogen vacancies due to the lack of nitrogen with the above group V elements. Will be able to. Since nitrogen vacancies are filled with the same group V raw material as nitrogen, carriers are not generated by this. As a result, n-type background carriers due to the presence of nitrogen vacancies can be reduced, and p-type electrical characteristics can be obtained more easily by introducing p-type carriers. Further, Group V elements other than nitrogen in the nitride compound semiconductor crystal containing In are in a minute amount enough to fill the vacancies in nitrogen, and no change in band gap energy occurs.

As described above, Group V elements other than nitrogen that are generally used in Group III-V include As, P, and Sb. FIG. 2 shows a report example of the decomposition characteristics of arsine (AsH ₃ ) as a raw material of As, phosphine (PH ₃ ) as a raw material of P, and trimethylantimony (TMSb) as a raw material of Sb (see Non-Patent Document 6). . In FIG. 2, the thermal decomposition characteristics of ammonia are also shown for comparison. 2, (a) shows the thermal decomposition characteristics of arsine, (b) shows the thermal decomposition characteristics of phosphine, (c) shows the thermal decomposition characteristics of trimethylantimony, and (d) shows ammonia. The thermal decomposition characteristics of are shown.

  As is apparent from FIG. 2, it can be seen that arsine, phosphine, and trimethylantimony are decomposed at a lower temperature than ammonia. Further, it should be noted that the decomposition of each material has occurred sufficiently even at a temperature of 600 ° C. or lower necessary for stably growing a nitride compound semiconductor containing InN. This indicates that when these group V source gases are supplied simultaneously when growing a nitride compound semiconductor containing In, nitrogen vacancies can be filled with the supplied group V atoms. Further, if the generation of nitrogen vacancies can be suppressed, n-type background carriers are reduced, and as a result, p-type doping becomes possible, and p-type electrical control can be performed stably.

  As the As raw material, trimethylarsine (TMAs), triethylarsine (TEAs), tertiarybutylarsine (TBAs), or trisdimethylaminoarsine (TDMAAs) having a decomposition temperature lower than that of arsine can be used. As the P raw material, trimethylphosphine (TMP), triethylphosphine (TEP), tertiarybutylphosphine (TBP), or trisdimethylaminophosphine (TDMAP) having a decomposition temperature lower than that of phosphine can be used. Furthermore, triethylantimony (TESb) and trisdimethylaminoantimony (TDMASb), which have a decomposition temperature lower than that of trimethylantimony, can be used as the raw material for Sb.

  Hereinafter, it demonstrates in detail using an Example.

[Example 1]
First, Example 1 will be described. In Example 1, the case of InGaN doped with Mg as a p-type nitride compound semiconductor crystal containing In will be described. Note that a metal organic chemical vapor deposition (MOCVD) method is used for crystal growth.

First, trimethylindium (TMIn) is used as a raw material of group III element In, and trimethylgallium (TMG) is used as a raw material of other group III element Ga. Further, ammonia (NH ₃ ) is used as a raw material for nitrogen, which is a group V element. Further, arsine is used as a Group V material other than nitrogen. Further, biscyclopentadienyl magnesium (Cp ₂ Mg) is used for p-type doping. Further, nitrogen is used as the carrier gas, the substrate is heated using a tansten heater, and the growth pressure is set to 9806.65 Pa.

  An intermediate layer made of AlN having a thickness of 50 nm is first formed on a substrate made of single crystal silicon at 1000 ° C., and the above-described p-type InGaN layer is formed on the intermediate layer. In addition, the p-type InGaN layer is formed at a temperature of 600 ° C. (substrate temperature), and is supplied to the above-described raw materials so as to have a layer thickness of about 1000 nm.

FIG. 3 shows a sequence relating to the change in substrate temperature and the supply of each source gas in the growth of each layer described above. First, in step 1, the substrate temperature is raised to 1000 ° C. In step 1, the supply of the source gas is stopped. Next, in step 2, the substrate temperature is maintained at 1000 ° C. for a predetermined time, and then in step 3, TMA and NH ₃ are supplied for a predetermined time in a state where the substrate temperature is maintained at 1000 ° C. Next, in step 4, the substrate temperature is lowered to 600 ° C. and only NH ₃ is supplied. Next, in step 5, TMI, TMG, NH ₃ , Cp ₂ Mg, and AsH ₃ are supplied for a predetermined time while the substrate temperature is maintained at 600 ° C. Next, in step 6, the substrate temperature is lowered from 600 ° C., and in this process, only NH ₃ is supplied for a predetermined time. Finally, in step 7, supply of all source gases is stopped, and the substrate temperature is lowered to room temperature (about 20 ° C.).

As a result of estimating the composition of the grown InGaN crystal from X-ray diffraction, it was confirmed that the In composition was 0.5. In other words, it was confirmed that the nitride compound semiconductor crystal containing In formed was In _0.5 Ga _0.5 N.

  In the above-described growth of p-type InGaN, by supplying a predetermined amount of arsine, the background carrier concentration is reduced, and p-type electrical characteristics can be obtained more easily.

This decrease in background carriers is due to the fact that the supplied arsine is thermally decomposed at a low temperature to become As and fills the vacancy of nitrogen. Moreover, the background carrier concentration in InGaN can be reduced to about 1 × 10 ¹⁵ cm ⁻³ by setting the supply amount of arsine to 0.1 sccm. The change in the background carrier concentration is evaluated by an InGaN layer formed without supplying Cp ₂ Mg. This electrical characteristic is evaluated by CV measurement. Other electrical characteristics described later are also evaluated by CV measurement. Sccm is a unit of flow rate, and indicates that a fluid at 0 ° C. and 1013 hPa flows 1 cm ³ per minute.

Further, the p-type carrier concentration in InGaN can be controlled by the supply amount of Cp ₂ Mg. When the supply amount of Cp ₂ Mg is changed from 0.01 to 0.05 sccm under a constant supply condition of an arsine flow rate of 0.1 sccm that can sufficiently reduce the background carrier concentration, the p-type carrier concentration is set to 2. Control was linearly and accurately in the range of 5 × 10 ¹⁶ to 1.25 × 10 ¹⁷ cm ⁻³ .

[Example 2]
Next, Example 2 will be described. Also in Example 2, the case of InGaN doped with Mg as a p-type nitride compound semiconductor crystal containing In will be described. In Example 2, phosphine (PH ₃ ) is used as a Group V material other than nitrogen.

First, trimethylindium (TMIn) is used as a raw material of group III element In, and trimethylgallium (TMG) is used as a raw material of other group III element Ga. Further, ammonia (NH ₃ ) is used as a raw material for nitrogen, which is a group V element. Cp ₂ Mg is used for p-type doping. Further, nitrogen is used as the carrier gas, the substrate is heated using a tansten heater, and the growth pressure is set to 9806.65 Pa. These conditions are the same as in Example 1 described above. In this embodiment, phosphine is used as a group V material other than nitrogen.

  In the above-described p-type InGaN, an intermediate layer made of AlN having a layer thickness of 50 nm is first formed on a substrate made of single crystal silicon on the condition of 1000 ° C., as in Example 1 described above. Form on the layer. In addition, the p-type InGaN layer is formed at a temperature of 600 ° C. (substrate temperature), and is supplied to the above-described raw materials so as to have a layer thickness of about 1000 nm.

FIG. 4 shows a sequence relating to the change in substrate temperature and the supply of each source gas in the growth of each layer described above. First, in step 1, the substrate temperature is raised to 1000 ° C. In step 1, the supply of the source gas is stopped. Next, in step 2, the substrate temperature is maintained at 1000 ° C. for a predetermined time, and then in step 3, TMA and NH ₃ are supplied for a predetermined time in a state where the substrate temperature is maintained at 1000 ° C. Next, in step 4, the substrate temperature is lowered to 600 ° C. and only NH ₃ is supplied. Next, in step 5, TMI, TMG, NH ₃ , Cp ₂ Mg, and PH ₃ are supplied for a predetermined time while the substrate temperature is maintained at 600 ° C. Next, in step 6, the substrate temperature is lowered from 600 ° C., and in this process, only NH ₃ is supplied for a predetermined time. Finally, in step 7, supply of all source gases is stopped, and the substrate temperature is lowered to room temperature.

  In the above-described growth of p-type InGaN, by supplying a predetermined amount of phosphine, the background carrier concentration is reduced, and p-type electrical characteristics can be obtained more easily.

This decrease in the background carriers is due to the fact that the supplied phosphine is P due to thermal decomposition at a low temperature, filling the nitrogen vacancies. Further, by setting the supply amount of phosphine to 5 sccm, the background carrier concentration in InGaN can be reduced to about 1 × 10 ¹⁵ cm ⁻³ . As described above, the change in the background carrier concentration is evaluated by an InGaN layer formed without supplying Cp ₂ Mg.

Further, when the supply amount of Cp ₂ Mg is changed from 0.01 to 0.05 sccm under a constant supply condition of a phosphine flow rate of 5 sccm that can sufficiently reduce the background carrier concentration, the p-type carrier concentration is set to 2. Control was linearly and accurately in the range of 5 × 10 ¹⁶ to 1.25 × 10 ¹⁷ cm ⁻³ .

[Example 3]
Next, Example 3 will be described. In Example 3, the case of InGaN doped with Mg as the p-type nitride compound semiconductor crystal containing In will be described. In Example 3, trimethylantimony (TMSb) is used as a Group V material other than nitrogen.

First, trimethylindium (TMIn) is used as a raw material of group III element In, and trimethylgallium (TMG) is used as a raw material of other group III element Ga. Further, ammonia (NH ₃ ) is used as a raw material for nitrogen, which is a group V element. Cp ₂ Mg is used for p-type doping. Further, nitrogen is used as the carrier gas, the substrate is heated using a tansten heater, and the growth pressure is set to 9806.65 Pa. These conditions are the same as in Example 1 described above. In this embodiment, trimethylantimony is used as a group V material other than nitrogen.

  In the above-described p-type InGaN, an intermediate layer made of AlN having a layer thickness of 50 nm is first formed on a substrate made of single crystal silicon on the condition of 1000 ° C., as in Example 1 described above. Form on the layer. In addition, the p-type InGaN layer is formed at a temperature of 600 ° C. (substrate temperature), and is supplied to the above-described raw materials so as to have a layer thickness of about 1000 nm.

FIG. 5 shows a sequence related to the change in substrate temperature and the supply of each source gas in the growth of each layer described above. First, in step 1, the substrate temperature is raised to 1000 ° C. In step 1, the supply of the source gas is stopped. Next, in step 2, the substrate temperature is maintained at 1000 ° C. for a predetermined time, and then in step 3, TMA and NH ₃ are supplied for a predetermined time in a state where the substrate temperature is maintained at 1000 ° C. Next, in step 4, the substrate temperature is lowered to 600 ° C. and only NH ₃ is supplied. Next, in step 5, TMI, TMG, NH ₃ , Cp ₂ Mg, and TMSb are supplied for a predetermined time while the substrate temperature is maintained at 600 ° C. Next, in step 6, the substrate temperature is lowered from 600 ° C., and only NH ₃ is supplied for a predetermined time in this process. Finally, in step 7, supply of all source gases is stopped, and the substrate temperature is lowered to room temperature.

  In the above-described growth of p-type InGaN, by supplying a predetermined amount of trimethylantimony, the background carrier concentration is reduced, and p-type electrical characteristics can be obtained more easily.

This decrease in background carriers is due to the fact that the supplied trimethylantimony is thermally decomposed at a low temperature to become P, filling the nitrogen vacancies. Moreover, the background carrier concentration in InGaN can be reduced to about 1 × 10 ¹⁵ cm ⁻³ by setting the supply amount of trimethylantimony to 0.5 sccm. As described above, the change in the background carrier concentration is evaluated by an InGaN layer formed without supplying Cp ₂ Mg.

Further, when the supply amount of Cp ₂ Mg was changed from 0.01 to 0.05 sccm under a constant supply condition of a trimethylantimony flow rate of 0.5 sccm that can sufficiently reduce the background carrier concentration, the p-type carrier concentration Can be controlled linearly and accurately in the range of 2.5 × 10 ¹⁶ to 1.25 × 10 ¹⁷ cm ⁻³ .

The ^reason why the V group source gas flow rates at which the background carrier concentration in Examples 1 to ^{3 is} reduced to about 1 × 10 ¹⁵ cm ⁻³ is different is due to the difference in thermal decomposition characteristics of the respective V group sources. As a result of evaluating the doped InGaN crystal by SIMS analysis, the concentration of As, P, and Sb was about 2 × 10 ¹⁹ cm ⁻³ .

  An object of the present invention is to realize p-type doping, which has been a problem when forming a nitride compound semiconductor crystal containing In. When forming a nitride compound semiconductor crystal containing In, nitrogen vacancies are generated, which become n-type background carriers, making it difficult to realize p-type electrical characteristics. In the present invention, a nitride compound semiconductor crystal containing In doped with a p-type impurity is formed while supplying another group V source gas different from nitrogen, thereby reducing nitrogen vacancies. It has a great effect on optical / electronic device manufacturing that enables characteristic control.

The present invention is not limited to the embodiment described above, and many modifications and combinations can be implemented by those having ordinary knowledge in the art within the technical idea of the present invention. It is obvious. For example, in the above-described embodiment, the In _0.5 Ga _0.5 N crystal has been described as an example. However, the present invention is not limited to this, and InAs having the same problem due to nitrogen vacancies, InGaN, InAlN, and InAlGaN having other compositions. However, it goes without saying that the same effect can be obtained. Moreover, not only MOCVD but also MBE may be used.

  The substrate is not limited to silicon, and may be a sapphire, SiC, and GaN substrate.

For example, when growing In _0.5 Ga _0.5 N using a sapphire substrate and using a V group material other than nitrogen (AsH ₃ , PH ₃ orTMSb) by MOCVD, as shown in the sequence of FIG. In step 1, the substrate temperature is raised to 1000 ° C. Next, after maintaining the substrate temperature at 1000 ° C. for a predetermined time in step 2, the substrate temperature is lowered to 600 ° C. in step 3. In steps 1 to 3, the supply of the source gas is stopped. Next, in Step 4, while maintaining the substrate temperature at 600 ° C., TMG and NH ₃ are supplied for a predetermined time. Next, in step 5, the substrate temperature is raised to 1000 ° C. while supplying only NH ₃ . In step 6, the substrate temperature is maintained at 1000 ° C. for a predetermined time, and the supply of TMG and NH ₃ is continued. Next, in step 7, the substrate temperature is lowered to 600 ° C. and only NH ₃ is supplied. Next, in step 8, with the substrate temperature maintained at 600 ° C., V group materials other than TMI, TMG, NH ₃ , Cp ₂ Mg, and nitrogen are supplied for a predetermined time. Next, in step 9, the substrate temperature is lowered from 600 ° C., and in this process, only NH ₃ is supplied for a predetermined time. Finally, in step 10, supply of all source gases is stopped and the substrate temperature is lowered to room temperature.

Further, in the case where In _0.5 Ga _0.5 N is grown using a SiC substrate and using a group V material (AsH ₃ , PH ₃ orTMSb) other than nitrogen by MOCVD, as shown in the sequence of FIG. In step 1, the substrate temperature is raised to 1000 ° C. In step 1, the supply of the source gas is stopped. Next, after maintaining the substrate temperature at 1000 ° C. for a predetermined time in step 2, TMA, TMG, and NH ₃ are supplied for a predetermined time with the substrate temperature maintained at 1000 ° C. in step 3. Next, in step 4, the substrate temperature is lowered to 600 ° C. and only NH ₃ is supplied. Next, in step 5, with the substrate temperature maintained at 600 ° C., V group materials other than TMI, TMG, NH ₃ , Cp ₂ Mg, and nitrogen are supplied for a predetermined time. Next, in step 6, the substrate temperature is lowered from 600 ° C., and only NH ₃ is supplied for a predetermined time in this process. Finally, in step 7, supply of all source gases is stopped, and the substrate temperature is lowered to room temperature.

In the case where In _0.5 Ga _0.5 N is grown using a GaN substrate by using a group V material (AsH ₃ , PH ₃ orTMSb) other than nitrogen by MOCVD, first, as shown in FIG. To step 2 to raise the substrate temperature to 1000 ° C. In step 1, the supply of the source gas is stopped, and in step 2, the supply of NH ₃ is started. Next, after maintaining the substrate temperature at 1000 ° C. for a predetermined time in step 3, the substrate temperature is lowered to 600 ° C. in step 4. In addition, the supply of NH ₃ is continued through steps 3 and 4. Next, in step 5, with the substrate temperature maintained at 600 ° C., V group materials other than TMI, TMG, NH ₃ , Cp ₂ Mg, and nitrogen are supplied for a predetermined time. Next, in step 6, the substrate temperature is lowered from 600 ° C., and only NH ₃ is supplied for a predetermined time in this process. Finally, in step 7, supply of all source gases is stopped, and the substrate temperature is lowered to room temperature.

  101... Substrate, 102... P-type nitride compound semiconductor crystal layer containing In.

Claims (4)

Heating the substrate;
Supplying at least an In raw material, ammonia, a Group V raw material other than nitrogen, and a p-type dopant raw material onto the substrate,
The method for producing a p-type nitride compound semiconductor crystal containing In, wherein the group V is selected from As, P, and Sb. In the manufacturing method of the p-type nitride compound semiconductor crystal containing In according to claim 1,
The method for producing a p-type nitride compound semiconductor crystal containing In, wherein the p-type dopant is Mg. In the manufacturing method of the p-type nitride compound semiconductor crystal containing In of Claim 1 or 2,
A p-type nitride compound semiconductor crystal containing In selected from InN, InGaN, InAlN, and InAlGaN is formed on the substrate. A method for producing a p-type nitride compound semiconductor crystal containing In. In the manufacturing method of the p-type nitride compound semiconductor crystal containing In of any one of Claims 1-3,
The substrate is made of a material selected from silicon, sapphire, SiC, and GaN. A method for producing a p-type nitride compound semiconductor crystal containing In, wherein:

Images