JP5678981B2 - Crystal manufacturing method - Google Patents

Description

  The present invention relates to a crystal manufacturing method.

  Currently, most of InGaAlN-based (group III nitride) devices used as purple-blue-green light sources are MO-CVD (metal organic chemical vapor deposition) or MBE ( It is produced by crystal growth using a molecular beam crystal growth method) or the like. When sapphire or SiC is used as a substrate, crystal defects due to large difference in thermal expansion coefficient and difference in lattice constant from group III nitride increase. For this reason, there is a problem that the device characteristics are poor, for example, it is difficult to extend the life of the light emitting device, or the operating power is increased.

  Furthermore, in the case of a sapphire substrate, since it is insulative, it is impossible to take out the electrode from the substrate side as in the conventional light emitting device, and it is necessary to take out the electrode from the nitride semiconductor surface side where the crystal has grown. . As a result, there is a problem that the device area is increased, leading to high costs. Further, the group III nitride semiconductor device fabricated on the sapphire substrate is difficult to separate the chip by cleavage, and it is not easy to obtain the resonator end face required for the laser diode (LD) by cleavage. For this reason, at present, resonator end faces are formed by dry etching, or resonator end faces are formed in a form close to cleavage after polishing the sapphire substrate to a thickness of 100 μm or less. Also in this case, it is impossible to easily separate the resonator end face from the conventional LD and the chip in a single process, resulting in a complicated process and an increase in cost.

  In order to solve these problems, it has been proposed to reduce crystal defects by performing selective lateral growth and other devices on a sapphire substrate for a group III nitride semiconductor film.

For example, in the document “Japan Journal of Applied Physics Vol. 36 (1997) Part 2, No. 12A, L 1568-1571” (hereinafter referred to as the first prior art), a laser diode (LD) as shown in FIG. It is shown. In the laser diode of FIG. 6, a GaN low temperature buffer layer 2 and a GaN layer 3 are sequentially grown on a sapphire substrate 1 by an MO-VPE (metal organic chemical vapor deposition) apparatus, and then a SiO ₂ mask 4 for selective growth is formed. To do. The SiO ₂ mask 4 is formed through a photolithography and etching process after depositing a SiO ₂ film by another CVD (chemical vapor deposition) apparatus. Next, when the GaN film 3 having a thickness of 20 μm is grown again on the SiO ₂ mask 4 by the MO-VPE apparatus, GaN is selectively grown in the lateral direction, and selective lateral growth is not performed. In comparison, crystal defects are reduced. Further, by introducing a modulation-doped strained superlattice layer (MD-SLS) 5 formed thereon, crystal defects are prevented from extending to the active layer 6. As a result, the device lifetime can be extended as compared with the case where the selective lateral growth and modulation-doped strained superlattice layer is not used.

In the case of the first prior art, it is possible to reduce crystal defects as compared with the case where the GaN film is not selectively grown in the lateral direction on the sapphire substrate. And the above-mentioned problems regarding cleavage still remain. Furthermore, the crystal growth by the MO-VPE apparatus is required twice with the SiO ₂ mask formation process in between, and a new problem that the process becomes complicated arises.

  As another method, for example, in a document “Applied Physics Letters, Vol. 73, No. 6, P. 832-834 (1998)” (hereinafter referred to as a second conventional technique), a GaN thick film substrate is used. Application is proposed. In the second prior art, after the selective lateral growth of 20 μm of the first prior art described above, a 200 μm thick GaN film is grown by an H-VPE (hydride vapor phase epitaxy) apparatus, and then this thickness is increased. The grown GaN film is polished from the sapphire substrate side to a thickness of 150 μm to produce a GaN substrate. Using the MO-VPE apparatus on this GaN substrate, crystal growth necessary for the LD device is sequentially performed to manufacture the LD device. As a result, in addition to the problem of crystal defects, it is possible to solve the above-described problems related to insulation and cleavage by using a sapphire substrate.

However, the process of the second conventional technique is more complicated than that of the first conventional technique, which further increases the cost. Further, when a GaN thick film having a thickness of 200 μm is grown by the second prior art method, the stress accompanying the difference in lattice constant and thermal expansion coefficient from sapphire, which is the substrate, is increased, causing the substrate to warp and crack. A new problem arises. Even if such a complicated process is performed, the crystal defect density can be reduced only to about 10 ⁶ / cm ² , and a practical semiconductor device cannot be obtained.

  In order to avoid this problem, Japanese Patent Application Laid-Open No. 10-256661 discloses that the thickness of the original substrate on which a thick film is grown (In Japanese Patent Application Laid-Open No. 10-256661, sapphire and spinel are most desirable) is set to 1 mm or more Has been proposed. By using a substrate having a thickness of 1 mm or more, even when a thick GaN film is grown to 200 μm, the substrate is not warped or cracked. However, such a thick substrate has a high cost of the substrate itself and needs to spend a lot of time for polishing, leading to an increase in the cost of the polishing process. That is, using a thick substrate increases the cost compared to using a thin substrate. When a thick substrate is used, the substrate is not warped or cracked after the thick GaN film is grown, but stress is relaxed in the polishing process, and warping or cracking occurs during polishing. For this reason, even if a thick substrate is used, a GaN substrate having a high crystal quality cannot be easily formed with a large area.

  On the other hand, in the document “Journal of Crystal Growth, Vol. It has been proposed to be used as a substrate. This technique is a technique for crystal growth of GaN from liquid Ga at a high temperature of 1400 to 1700 ° C. and an ultrahigh pressure of several tens of kbar. In this case, a group III nitride semiconductor film necessary for the device can be grown using the bulk-grown GaN substrate. Therefore, the GaN substrate can be provided without complicating the process as in the first and second conventional techniques.

  However, in the third prior art, there is a problem that crystal growth at high temperature and high pressure is required, and a reaction vessel that can withstand the growth becomes extremely expensive. In addition, even with such a growth method, there is a problem that the size of the obtained crystal is at most about 1 cm, which is too small for practical use of the device.

As a technique for solving this problem of GaN crystal growth at high temperature and high pressure, the document “Chemistry of Materials Vol. 9 (1997) P.413-416” (hereinafter referred to as the fourth conventional technique) includes: A GaN crystal growth method using Na, which is an alkali metal, as a flux has been proposed. In this method, sodium azide (NaN ₃ ) and metal Ga are used as a flux and a raw material, and sealed in a stainless steel reaction vessel (inner dimensions; inner diameter = 7.5 mm, length = 100 mm) in a nitrogen atmosphere, and the reaction A GaN crystal is grown by holding the container at a temperature of 600 to 800 ° C. for 24 to 100 hours. In the case of the fourth prior art, crystal growth at a relatively low temperature of about 600 to 800 ° C. is possible, and the pressure in the container is at most about 100 kg / cm ^2, which is higher than that of the third prior art. It is a feature that can be lowered. However, the problem with this method is that the crystal size obtained is small enough to be less than 1 mm. This size is too small for practical use of the device, as in the case of the third prior art.

  The present invention provides group III nitride crystals and high-performance group III nitride semiconductor devices that are inexpensive and practical without complicating the process, and prevents alkali metal condensation outside the reaction vessel. The purpose is to be able to.

To achieve the above object, the present invention is, in a counter-reaction container unit, by using a nitrogen material introduced from the outside of the alkali metal and the melt mixture containing at least group III metal the counter-reaction container unit, group III when growing a nitride crystal, a crystal manufacturing method, wherein the nitrogen raw material before outside of Kihan reaction container unit causes re-evaporated alkali metal condenses region passes.

  As described above, according to the present invention, a III-nitride crystal having a practical size and a high-performance III-nitride semiconductor device can be provided inexpensively without complicating the process, and a reaction vessel It is possible to prevent the condensation of alkali metal outside.

It is a figure which shows the 1st structural example of the crystal growth apparatus which concerns on this invention. It is a figure which shows the 2nd structural example of the crystal growth apparatus based on this invention. It is a figure which shows the 3rd structural example of the crystal growth apparatus based on this invention. It is a figure which shows the 4th structural example of the crystal growth apparatus based on this invention. It is a figure which shows the structural example of the semiconductor device which concerns on this invention. It is a figure which shows the conventional laser diode.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. The present invention grows a group III nitride crystal in a first reaction vessel using a mixed melt containing an alkali metal and at least a group III metal and a nitrogen raw material introduced from the outside of the first reaction vessel. In this case, the alkali metal vapor is confined in the first reaction vessel.

  In the crystal growth method of the present invention, in the first reaction vessel, there is a mixed melt containing an alkali metal and at least a group III metal, and the temperature of the first reaction vessel is controlled so that crystal growth is possible. Yes. The nitrogen raw material is introduced from the outside of the first reaction vessel, and the alkali metal, the group III metal, and the nitrogen raw material react to cause group III nitride crystal growth. Here, the nitrogen raw material refers to nitrogen molecules, atomic nitrogen, or nitrogen molecules or atomic nitrogen generated from nitrogen-containing compounds.

  In the temperature region where the group III nitride crystal grows, the alkali metal has a certain vapor pressure. In the present invention, the alkali metal vapor is confined in the first reaction vessel so that it does not diffuse out of the first reaction vessel.

  In particular, the present invention relates to a group III nitride crystal using a mixed melt containing an alkali metal and at least a group III metal in a first reaction vessel and a nitrogen raw material introduced from the outside of the first reaction vessel. Is characterized in that the alkali metal vapor does not block the region where the nitrogen source passes from the outside of the first reaction vessel into the first reaction vessel.

  Here, to prevent the alkali metal vapor from blocking the region where the nitrogen raw material passes from the outside of the first reaction vessel into the first reaction vessel, only that the alkali metal does not condense in that region. It also includes removing alkali metal (eg, mechanically) condensed in the region.

  In order to prevent the aggregation of the alkali metal as described above, the present invention introduces the mixed melt containing the alkali metal and at least a group III metal from the outside of the first reaction vessel in the first reaction vessel. When a group III nitride crystal is grown using a nitrogen source, the temperature above the surface of the mixed melt containing an alkali metal and at least a group III metal is controlled to a temperature that does not condense the alkali metal vapor. It is characterized by. That is, the temperature above the surface of the mixed melt in the first reaction vessel is equal to or higher than the temperature of the mixed melt including the surface of the mixed melt.

  FIG. 1 is a diagram showing a first configuration example of the crystal growth apparatus of the present invention. In the example of FIG. 1, Na as an alkali metal and metal Ga as a substance containing at least a group III metal element are accommodated in the first reaction vessel 101, and a group III nitride crystal grows in them. The mixed melt 102 is formed in the temperature region.

Here, the first reaction vessel 101 is made of stainless steel, and the space region in the first reaction vessel 101 is filled with nitrogen gas (N ₂ ) 103 as a substance containing at least nitrogen element. The nitrogen gas 103 can be supplied from the outside of the first reaction vessel 101 through the nitrogen supply pipe 104. In order to adjust the nitrogen pressure, the apparatus shown in FIG. ing. The pressure adjustment mechanism 105 includes, for example, a pressure sensor and a pressure adjustment valve. The nitrogen pressure in the first reaction vessel 101 is controlled to, for example, 50 atm by the pressure adjustment mechanism 105.

  In the crystal growth apparatus of FIG. 1, the mixed melt 102 or mixed melt is disposed outside the region of the first reaction vessel 101 where the mixed melt 102 of alkali metal Na and group III metal Ga is held. A first heating device 106 is provided on the surface of the liquid 102 so that the temperature of the group III nitride can be controlled to allow crystal growth.

  Furthermore, in the crystal growth apparatus of FIG. 1, a second heating device 107 is provided above the first heating device 106 so that the temperature above the surface of the mixed melt 102 can be controlled.

  In such a configuration, the first heating device 106 controls the temperature at which the group III nitride crystal grows (for example, 750 ° C.), whereby the alkali metal Na and the group III metal raw material Ga are mixed melt. 102 is formed. Here, the second heating device 107 causes the temperature above the surface of the mixed melt 102 made of alkali metal Na and group III metal raw material Ga to be equal to or higher than the temperature of the mixed melt 102. The temperature at the top of one reaction vessel 101 is controlled. In this state, Ga, which is a group III metal, is supplied from the mixed melt 102 and kept constant at the growth temperature, so that a GaN crystal as a group III nitride is crystallized in the mixed melt 108 and the mixed melt surface 109. grow up.

  In the crystal growth apparatus of FIG. 1, nitrogen gas reacts with Ga in the mixed melt 108 of Na and Ga and the mixed melt surface 109, or the nitrogen component in the melt supplied from the nitrogen gas. By reacting Ga with Ga, a continuous GaN crystal grows and a crystal with a large crystal size can be obtained.

  Further, in the crystal growth apparatus of FIG. 1, the temperature above the surface of the mixed melt 102 made of Na which is an alkali metal and Ga which is a group III metal raw material is equal to or higher than the temperature of the mixed melt 102. Since the temperature of the upper part of the first reaction vessel 101 is controlled by the second heating device 107, condensation of Na on the upper part of the first reaction vessel 101 can be prevented. That is, since the temperature of the upper part of the mixed melt 102 is equal to or higher than the temperature of the mixed melt 102, the condensation of Na on the upper part of the first reaction vessel 101 can be prevented. As a result, it is possible to prevent Na from condensing on the nitrogen supply pipe 104. That is, it is possible to prevent inhibition of nitrogen introduction due to the condensation of Na into the nitrogen supply pipe 104. In addition, the composition of the mixed melt 102 between the alkali metal Na and the group III metal Ga hardly changes, and stable crystal growth is possible. Here, alkali metal (alkali metal vapor) Na is confined in the first reaction vessel 101.

  In other words, when the temperature above the surface of the mixed melt 102 is lower than the temperature of the mixed melt 102, condensation of Na on the inner wall of the first reaction vessel 101 and the nitrogen supply pipe 104 occurs. End up. As a result, the composition of the alkali metal Na and the group III metal Ga in the mixed melt 102 changes or the nitrogen supply pipe 104 is blocked by Na, which makes it difficult to supply nitrogen. In the present invention, the temperature above the first reaction vessel 101 is controlled by the second heating device 107 so that the temperature above the surface of the mixed melt 102 is equal to or higher than the temperature of the mixed melt 102. Thus, it is possible to avoid such a situation.

  Further, in the crystal growth apparatus of FIG. 1, the temperature of the region where the nitrogen source passes from the outside of the first reaction vessel 101 into the first reaction vessel 101 can also be controlled.

  FIG. 2 is a diagram showing a second configuration example of the crystal growth apparatus of the present invention. In the crystal growth apparatus of FIG. 2, in the crystal growth apparatus of FIG. To the temperature of the region passing through the first reaction vessel 101 is controlled.

  That is, in the crystal growth apparatus of FIG. 2, a nitrogen supply pipe is used to control the temperature of the region (that is, the nitrogen supply pipe 104) through which the nitrogen source passes from the outside of the first reaction container 101 into the first reaction container 101. A third heating device 110 is provided outside 104.

  In the crystal growth apparatus of FIG. 2, the temperature of the nitrogen supply pipe 104 can be controlled by the third heating apparatus 110. That is, by heating the nitrogen supply pipe 104 by the third heating device 110, it is possible to prevent the alkali metal from condensing into the nitrogen supply pipe 104 more effectively than the crystal growth apparatus of FIG. As a result, nitrogen can be introduced more smoothly into the reaction vessel 101, and stable crystal growth becomes possible.

  As described above, in the crystal growth apparatus of FIG. 2, by heating the region (nitrogen supply pipe 104) through which the nitrogen raw material passes from the outside of the first reaction vessel 101 into the first reaction vessel 101, Condensation to that region (nitrogen supply pipe 104) is prevented. As described above, in addition to preventing the alkali metal from condensing in the region (the nitrogen supply pipe 104) through which the nitrogen material passes, the alkali metal adsorbed in this region (the nitrogen supply pipe 104) is removed (for example, mechanically). However, considering the structure on the apparatus, the structure such as the crystal growth apparatus in FIG. 2 more easily satisfies the original function. Further, since the temperature of the region through which the nitrogen material passes (nitrogen supply pipe 104) can be controlled as in the crystal growth apparatus of FIG. 2, the alkali metal is condensed in that region (nitrogen supply pipe 104). Even in this case, it is possible to re-evaporate the agglomerated alkali metal by heating the region (nitrogen supply pipe 104).

  In addition to the configuration example of the crystal growth apparatus of FIGS. 1 and 2, it is possible to realize a function of confining alkali metal vapor in the first reaction vessel. For example, a second reaction vessel is provided outside the first reaction vessel, a nitrogen material is introduced from the outside of the second reaction vessel, and the first reaction vessel permeates the nitrogen material from the second reaction vessel. However, a structure in which alkali metal vapor is confined can also be employed.

  In such a configuration, the nitrogen raw material is introduced into the second reaction vessel from the outside of the second reaction vessel. There is a mixed melt containing an alkali metal and at least a group III metal inside the first reaction vessel, and the nitrogen raw material is introduced into the first reaction vessel through the second reaction vessel. The alkali metal, the group III metal, and the nitrogen raw material react in the container, so that the group III nitride crystal grows. In the temperature region where the group III nitride crystal grows, the alkali metal has a certain vapor pressure, and the alkali metal vapor is confined in the first reaction vessel.

  FIG. 3 is a diagram showing a third configuration example of the crystal growth apparatus of the present invention. In the crystal growth apparatus of FIG. 3, a second reaction vessel 111 is provided outside the first reaction vessel 101, and a second A nitrogen raw material is introduced from the outside of the reaction vessel 111, and the first reaction vessel 101 has a structure in which alkali metal vapor is confined while permeating the nitrogen raw material from the second reaction vessel 111.

  That is, in the crystal growth apparatus of FIG. 3, the second reaction vessel 111 is provided outside the first reaction vessel 101. There is a lid 112 at the top of the first reaction vessel 101. Here, the material of the first reaction vessel 101 is BN (boron nitride), and the second reaction vessel 111 is made of stainless steel.

The first reaction vessel 101 contains Na as an alkali metal and metal Ga as a substance containing at least a group III metal element, which are mixed and melted in a temperature region where a group III nitride crystal grows. A liquid 102 is formed. Nitrogen gas (N ₂ ) as a substance containing at least a nitrogen element is filled in the space region 103 in the first reaction vessel 101 and the space region 113 in the second reaction vessel 111. This nitrogen gas can be supplied into the second reaction vessel 111 from the outside of the second reaction vessel 111 through the nitrogen supply pipe 104. Further, the lid 112 of the first reaction vessel 101 has a minute gap that allows nitrogen gas to pass therethrough, and the nitrogen gas passes through the gap from the second reaction vessel 111 into the first reaction vessel 101. Can be supplied.

  In order to adjust the nitrogen pressure, the apparatus of FIG. 3 is provided with a pressure adjusting mechanism 105. The pressure adjustment mechanism 105 includes, for example, a pressure sensor and a pressure adjustment valve. By the pressure adjustment mechanism 105, the nitrogen pressure in the second reaction vessel 111 and the first reaction vessel 101 is, for example, 50. It is controlled to atmospheric pressure.

  In the crystal growth apparatus of FIG. 3, group III nitride can be grown on the outside of the second reaction vessel 111 in the mixed melt 102 in the first reaction vessel 101 or on the surface of the mixed melt 102. A heating device 116 is provided so that the temperature can be controlled at a proper temperature.

  In such a configuration, the molten melt 102 of Na, which is an alkali metal, and Ga, which is a group III metal raw material, is controlled by the heating device 116 at a temperature at which the group III nitride crystal grows (for example, 750 ° C.). Is formed. In this state, Ga, which is a group III metal, is supplied from the mixed melt 102 and kept constant at the growth temperature, so that a GaN crystal as a group III nitride is crystallized in the mixed melt 108 and the mixed melt surface 109. grow up.

  In the crystal growth apparatus of FIG. 3, nitrogen gas reacts with Ga in the mixed melt of Na and Ga and the mixed melt surface 109, or the nitrogen component in the melt supplied from the nitrogen gas. By reacting Ga with Ga, a continuous GaN crystal grows and a crystal with a large crystal size can be obtained.

  By the way, in the crystal growth apparatus of FIG. 3, the first reaction vessel 101 and its lid 112 are provided so that most of the alkali metal in the first reaction vessel 101 can be confined in the first reaction vessel 101. It becomes. Thereby, the variation of the composition of the alkali metal and the group III metal is suppressed, and the group III nitride crystal can be grown with good controllability. At this time, condensation of alkali metal into the nitrogen supply pipe 104 can also be suppressed.

  Further, as described in the crystal growth apparatus of FIG. 1, the temperature above the surface of the mixed melt 102 made of Na, which is an alkali metal, and Ga, which is a group III metal material, is equal to or higher than the temperature of the mixed melt 102. In addition, when the temperature in the first reaction vessel 101 is controlled, it is possible to more reliably prevent diffusion due to condensation or the like of the alkali metal other than the mixed melt 102.

  Moreover, in the crystal growth apparatus of FIG.1, FIG.2, FIG.3, a nitrogen raw material is used from the horizontal direction of the 1st reaction container 101 or the 2nd reaction container 111, or a lower side rather than a horizontal direction. It can also be introduced into the reaction vessel 101 or 111.

  FIG. 4 is a diagram showing a fourth configuration example of the crystal growth apparatus of the present invention. In the crystal growth apparatus of FIG. 4, a nitrogen supply pipe 104 is connected to the lower side of the second reaction vessel 111. Therefore, nitrogen gas that is a nitrogen raw material is supplied from the lower side of the second reaction vessel 111. The inventor of the present application has experimentally confirmed that the alkali metal that has become vapor condenses more in the upper part of the reaction vessel, and nitrogen gas is introduced from the lower side as in the crystal growth apparatus of FIG. Thus, it is possible to more reliably prevent alkali metal condensation on the nitrogen supply pipe 104. As a result, nitrogen gas can be introduced more reliably, and crystal growth controllability (control of nitrogen pressure) can be enhanced.

  In the example of FIG. 4, nitrogen gas is introduced from the lower side of the second reaction vessel 111, but the introduction direction of the nitrogen gas is lower than the horizontal direction with respect to the second reaction vessel 111. The effects described above can be obtained.

  4 is applied to the configuration of the crystal growth apparatus of FIG. 3, it can also be applied to the configuration of the crystal growth apparatus of FIG. 1 or FIG. That is, in this case, the nitrogen raw material is introduced into the reaction vessel 101 or 111 from the horizontal direction of the first reaction vessel 101 or the second reaction vessel 111 or from the lower side of the horizontal direction. The same effect as that obtained in the crystal growth apparatus of FIG. 4 can be obtained.

  In the above example, Na is used as a low melting point and high vapor pressure metal (alkali metal), but potassium (K) or the like may be used instead of Na. That is, as the alkali metal, any alkali metal can be used as long as it becomes a melt at the temperature at which the group III nitride crystal is grown.

  In the above example, Ga is used as a substance containing at least a group III metal element. However, in addition to Ga, a simple metal such as Al or In, or a mixture or alloy thereof may be used. it can.

In the above example, nitrogen gas is used as the substance containing at least nitrogen element. However, other than nitrogen gas, a gas such as NH ₃ can also be used.

  In the above example, the first reaction vessel 101 is made of stainless steel. However, as the first reaction vessel 101, it is possible to grow a group III nitride crystal by shutting off the atmosphere from the outside. Any material made of any material can be used as long as it can withstand temperature and pressure and does not react with an alkali metal and does not elute as an impurity when the group III nitride crystal is grown.

  By using the above-mentioned crystal growth apparatuses (that is, the crystal growth apparatuses as shown in FIG. 1, FIG. 2, FIG. 3, or FIG. 4), a group III nitride crystal is grown, so that the crystal quality is high. A group III nitride crystal large enough to produce a device can be provided at low cost.

As an example of a method for growing a group III nitride crystal according to the present invention, Ga is used as a group III metal, nitrogen gas is used as a nitrogen raw material, Na is used as a flux, the temperature of the reaction vessel and the flux vessel is 750 ° C., and the nitrogen pressure is 50 kg. / Cm ² G to be constant. Under such conditions, GaN crystals can be grown.

  In addition, a group III nitride semiconductor device can be manufactured using a group III nitride crystal grown by the growth method of the present invention.

  FIG. 5 is a diagram showing a configuration example of a semiconductor device according to the present invention. In the example of FIG. 5, the semiconductor device is configured as a semiconductor laser. Referring to FIG. 5, in this semiconductor device, an n-type AlGaN cladding layer 302, an n-type GaN guide layer 303 are formed on an n-type GaN substrate 301 using a group III nitride crystal grown in the manner described above. An InGaN MQW (multiple quantum well) active layer 304, a p-type GaN guide layer 305, a p-type AlGaN cladding layer 306, and a p-type GaN contact layer 307 are sequentially grown. As this crystal growth method, a thin film crystal growth method such as MO-VPE (metal organic chemical vapor deposition) method or MBE (molecular beam epitaxy) method can be used.

Next, a ridge structure is formed in the laminated film of GaN, AlGaN, and InGaN, and the SiO ₂ insulating film 308 is formed in a state where only the contact region is drilled, and the p-side ohmic electrode Al / Ni 309 and the n-side ohmic are formed on the upper and lower parts, respectively. The electrode Al / Ti 310 is formed to constitute the semiconductor device (semiconductor laser) of FIG.

  By injecting current from the p-side ohmic electrode Al / Ni 309 and the n-side ohmic electrode Al / Ti 310 of this semiconductor laser, this semiconductor laser oscillates and can emit laser light in the direction of arrow A in FIG. .

  Since this group III nitride crystal (GaN crystal) of the present invention is used as the substrate 301, this semiconductor laser has few crystal defects in the semiconductor laser device, has a large output operation and a long life. Further, since the GaN substrate 301 is n-type, the electrode 310 can be formed directly on the substrate 301, and two electrodes on the p side and the n side can be formed from the surface as in the first prior art (FIG. 6). It is not necessary to take out only, and it is possible to reduce the cost.

  Furthermore, in the semiconductor device of FIG. 5, the light emitting end face can be formed by cleavage, and in combination with chip separation, a high-quality device can be realized at low cost.

101 First reaction vessel 102 Mixed melt 103 Nitrogen gas 104 Nitrogen supply pipe 105 Pressure adjusting mechanism 106 First heating device 107 Second heating device 108 Mixed melt 109 Mixed melt surface 110 Third heating device 111 Second reaction vessel 112 Lid 116 Heating device 301 n-type GaN substrate 302 n-type AlGaN cladding layer 303 n-type GaN guide layer 304 InGaN MQW (multiple quantum well) active layer 305 p-type GaN guide layer 306 p-type AlGaN cladding layer 307 p-type GaN contact layer 308 SiO ₂ insulating film 309 p-side ohmic electrode Al / Ni
310 n-side ohmic electrode Al / Ti

Japanese Patent Laid-Open No. 10-256661

Japan Journal of Applied Physics Vol. 36 (1997) Part 2, no. 12A, L1568-1571 Applied Physics Letters, Vol. 73, no. 6, P.I. 832-834 (1998) Journal of Crystal Growth, Vol. 189/190, p. 153-158 (1998) Chemistry of Materials Vol. 9 (1997) P.A. 413-416

Claims (2)

In varus reaction container vessel, the alkali metal and the melt mixture containing at least group III metal with a nitrogen material introduced from the outside of the anti-reaction container unit, when growing the group III nitride crystal, before Kihan A method for producing a crystal comprising re-evaporating an alkali metal condensed in a region through which the nitrogen raw material passes outside a reaction vessel. 2. The crystal manufacturing method according to claim 1 , wherein the alkali metal is re-evaporated by heating a region through which the nitrogen raw material passes.

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