JP2007173854A - Method of heat treating nitride compound semiconductor layer, and method of manufacturing semiconductor element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat treating method of a nitride compound semiconductor layer which enables a reduction in the resistance and activation of the semiconductor layer doped with p-type impurities at a temperature lower than that in a conventional technique. <P>SOLUTION: This heat treating method of the nitride compound semiconductor layer, makes the semiconductor layer doped with p-type impurities heat at the temperature of from 200°C or more to 1,200°C or less, in any one kind of ambient atmosphere of (A) the atmosphere, (B) an ambient atmosphere supplied with oxygen gas and hydrogen gas, (C) an ambient atmosphere supplied with oxygen gas and steam, (D) an ambient atmosphere supplied with oxygen gas, hydrogen gas, and steam, (E) an inert gas ambient atmosphere containing steam, and (F) a reduced pressure ambient atmosphere containing steam. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a nitride compound semiconductor layer heat treatment method and a semiconductor device manufacturing method.

  In recent years, gallium nitride-based compound semiconductors such as GaN, AlGaN mixed crystals, or AlInGaN mixed crystals are promising as constituent materials for semiconductor elements that can emit light from the visible region to the ultraviolet region. In particular, since the light emitting diode (LED: Light Emitting Diode) using a gallium nitride compound semiconductor has been put into practical use, it has attracted a great deal of attention. In addition, the realization of a semiconductor laser (LD: Laser Diode) using a gallium nitride compound semiconductor has been reported, and applications such as a light source of an optical disk device are expected.

By the way, when the gallium nitride compound semiconductor layer to which the p-type impurity is added is formed based on the vapor phase growth method, the gallium nitride compound semiconductor layer is not p-type as it is, and the resistivity is 10 ⁸ Ω. A semi-insulating layer having a high resistance of cm or more, i.e., an i-type compound semiconductor layer.

JP-A-2-257679 Japanese Patent No. 2540791

  A means for reducing the resistance of such a high-resistance i-type compound semiconductor layer to form a p-type compound semiconductor layer is known from, for example, Japanese Patent Laid-Open No. 2-257679. In the technique disclosed in this patent publication, the surface of an i-type gallium nitride compound semiconductor layer obtained by doping Mg as a p-type impurity is irradiated with an electron beam, whereby the gallium nitride compound semiconductor layer is formed. Reduce the resistance of the surface. However, in such a method, only the surface of the gallium nitride compound semiconductor layer can be reduced in resistance, and a long processing time is required for scanning the electron beam. There is a problem that it is difficult to uniformly reduce the resistance of the gallium compound semiconductor layer.

Japanese Patent No. 2540791 discloses that a gallium nitride compound semiconductor doped with a p-type impurity is grown by vapor phase epitaxy, and then 400 ° C or higher, and 600 ° C or higher for obtaining a practical carrier concentration. A technique for performing a heat treatment at a temperature of is disclosed. The heat treatment atmosphere is a vacuum or inert gas atmosphere that does not contain hydrogen atoms such as NH ₃ and H ₂ , and the heat treatment time is about 10 to 20 minutes.

However, when a semiconductor laser is manufactured, the higher the heat treatment temperature, the easier the diffusion of p-type impurities such as Mg or the like, or the steepness of the interface in the superlattice structure due to the diffusion of In tends to collapse. considered, for example, an increase in the threshold current I _th, such a short life, deterioration of the active layer is likely to proceed.

Furthermore, when heat treatment is performed at a high temperature, the surface of the gallium nitride compound semiconductor layer is deteriorated due to the dissociation of nitrogen atoms. In order to prevent the occurrence of such a phenomenon, a technique for forming a cap layer on the surface of a gallium nitride compound semiconductor layer is also disclosed in Japanese Patent Publication No. 2540791. However, the materials constituting the cap layer are Ga _x Al _1-x N (0 ≦ X ≦ 1), AlN, Si ₃ N ₄ , and SiO _2. In addition, it must be removed from the surface of the gallium nitride-based compound semiconductor layer, and there is a problem that the number of processes is increased.

  Accordingly, an object of the present invention is to provide a nitride compound semiconductor layer in which resistance and activation of a nitride compound semiconductor layer to which a p-type impurity is added can be performed at a lower temperature than in the prior art. And a method of manufacturing a semiconductor element to which the nitride compound semiconductor layer heat treatment method is applied.

In order to achieve the above object, the nitride compound semiconductor layer heat treatment method according to the first aspect of the present invention comprises a nitride compound semiconductor layer to which a p-type impurity is added, having a temperature of 200 ° C. or higher and lower than 400 ° C. Preferably, the temperature is 225 ° C or higher and lower than 400 ° C, more preferably 250 ° C or higher and lower than 400 ° C, still more preferably 300 ° C or higher and lower than 400 ° C, and the temperature is 100 minutes or longer, preferably 200 minutes or longer. Preferably heating is 500 minutes or more, more preferably 20 hours or more, more preferably 30 hours or more, still more preferably 3 × 10 ³ minutes (50 hours) or more, and even more preferably 1 × 10 ² hours or more. Features.

In order to achieve the above object, a method of manufacturing a semiconductor device according to the first aspect of the present invention is a method of manufacturing a nitride compound semiconductor layer to which a p-type impurity is added at 200 ° C. or more and less than 400 ° C., preferably 225. ° C or higher and lower than 400 ° C, more preferably 250 ° C or higher and lower than 400 ° C, still more preferably 300 ° C or higher and lower than 400 ° C, 100 minutes or longer, preferably 200 minutes or longer, more preferably 500 And more preferably 20 hours or more, more preferably 30 hours or more, even more preferably 3 × 10 ³ minutes (50 hours) or more, and even more preferably 1 × 10 ² hours or more. Features.

In order to achieve the above object, the nitride compound semiconductor layer heat treatment method according to the second aspect of the present invention uses a nitride compound semiconductor layer to which a p-type impurity is added as a coefficient α = 1.04 × 10 ^4. Where the coefficient ln (D ₀ ) = 53 and the carrier density of the nitride compound semiconductor layer after heat treatment is C (unit: cm ⁻³ ), the heating temperature T (unit: K) and the heating time t (unit: min) ) Is t ≧ 100, preferably t ≧ 200, more preferably t ≧ 500, even more preferably t ≧ 2 × 10 ³ , and the condition of the following formula (1) is satisfied: It is characterized by heat treatment.
T ≧ α / [ln (√t) + ln (D ₀ ) −ln (C)] (1)

In order to achieve the above object, a method of manufacturing a semiconductor device according to the second aspect of the present invention uses a nitride compound semiconductor layer to which a p-type impurity is added as a coefficient α = 1.04 × 10 ³ and a coefficient ln. (D ₀ ) = 53, where the carrier density of the nitride compound semiconductor layer after heat treatment is C (unit: cm ⁻³ ), the heating temperature T (unit: K) and the heating time t (unit: minute) are: heat treatment in a state where t ≧ 100, preferably t ≧ 200, more preferably t ≧ 500, and even more preferably t ≧ 2 × 10 ³ , and the condition of the above formula (1) is satisfied. It is characterized by including.

In the nitride compound semiconductor layer heat treatment method or semiconductor element manufacturing method according to the second aspect of the present invention (hereinafter, these may be collectively referred to as the method according to the second aspect of the present invention). Further, the heating temperature T (K) is set to 473 (K) ≦ T <673 (K), preferably 498 (K) ≦ T <673 (K), more preferably 523 (K) ≦ T <673 (K). ), More preferably, it is preferable to satisfy the condition of 573 (K) ≦ T <673 (K). If the heating temperature T is expressed in Celsius temperature, the heating temperature is 200 ° C. or higher and lower than 400 ° C., preferably 225 ° C. or higher and lower than 400 ° C., more preferably 250 ° C. or higher and lower than 400 ° C., and much more. The temperature is preferably 300 ° C or higher and lower than 400 ° C. Further, the carrier density C of the nitride compound semiconductor layer after the heat treatment is 1.0 × 10 ¹⁷ cm ⁻³ or more, preferably 3.0 × 10 ¹⁷ cm ⁻³ or more, more preferably 5.0 × 10 ¹⁷ cm. ^-3 or more, still more preferably 1.0 × 10 ¹⁸ cm ^-3 or more.

The nitride compound semiconductor layer heat treatment method or semiconductor element manufacturing method according to the first aspect of the present invention (hereinafter, these may be collectively referred to as the method according to the first aspect of the present invention), or In the method according to the second aspect of the present invention, the heating atmosphere can be an atmospheric atmosphere (the pressure may be any of atmospheric pressure, a reduced pressure state, and a pressurized state). Alternatively, the heating atmosphere can be an atmosphere to which at least oxygen gas is supplied. In this case, the heating atmosphere may be an atmosphere to which only oxygen gas is supplied, or oxygen gas and hydrogen gas are supplied. Or an atmosphere supplied with oxygen gas and water vapor, or an atmosphere supplied with oxygen gas, hydrogen gas and water vapor, or further inert to them. It may be an atmosphere supplied with gas. Alternatively, the heating atmosphere can be an inert gas atmosphere or a reduced-pressure atmosphere having a pressure lower than atmospheric pressure. In this case, the heating atmosphere may contain water vapor. Here, examples of the inert gas include nitrogen (N ₂ ) gas, helium (He) gas, neon (Ne) gas, argon (Ar) gas, or a mixed gas of these gases. When supplying oxygen gas and hydrogen gas, or when supplying oxygen gas, hydrogen gas and water vapor, the ratio of hydrogen gas in the mixed gas of oxygen gas and hydrogen gas is the lower limit of the combustion range (4% by volume). ) Must be less than Further, the supply ratio of oxygen gas / water vapor and the ratio of water vapor in the inert gas atmosphere or the reduced pressure atmosphere are essentially arbitrary.

In order to achieve the above object, a nitride compound semiconductor layer heat treatment method according to the third aspect of the present invention includes a nitride compound semiconductor layer to which a p-type impurity is added.
(A) Atmosphere,
(B) an atmosphere supplied with oxygen gas and hydrogen gas;
(C) an atmosphere supplied with oxygen gas and water vapor;
(D) an atmosphere supplied with oxygen gas, hydrogen gas, and water vapor;
(E) an inert gas atmosphere containing water vapor, and
(F) a reduced-pressure atmosphere containing water vapor and having a pressure lower than atmospheric pressure;
It is characterized by heating at a temperature of 200 ° C. or more and 1200 ° C. or less in an atmosphere of any one of the above.

In order to achieve the above object, a method of manufacturing a semiconductor device according to the third aspect of the present invention includes a nitride compound semiconductor layer to which a p-type impurity is added,
(A) Atmosphere,
(B) an atmosphere supplied with oxygen gas and hydrogen gas;
(C) an atmosphere supplied with oxygen gas and water vapor;
(D) an atmosphere supplied with oxygen gas, hydrogen gas, and water vapor;
(E) an inert gas atmosphere containing water vapor, and
(F) a reduced-pressure atmosphere containing water vapor and having a pressure lower than atmospheric pressure;
And heating at a temperature of 200 ° C. or higher and 1200 ° C. or lower in an atmosphere of any one of the above.

  The nitride compound semiconductor layer heat treatment method or semiconductor element manufacturing method according to the third aspect of the present invention (hereinafter, these may be collectively referred to as the method according to the third aspect of the present invention). , The ratio of hydrogen gas in the mixed gas of oxygen gas and hydrogen gas in the atmosphere supplied with oxygen gas and hydrogen gas or in the atmosphere supplied with oxygen gas, hydrogen gas and water vapor is the lower limit value of the combustion range ( Less than 4% by volume). Further, the supply ratio of oxygen gas / water vapor in the atmosphere supplied with oxygen gas and water vapor, and the ratio of water vapor in the inert gas atmosphere or the reduced pressure atmosphere are essentially arbitrary. In addition, the atmospheres (A) to (E) may be in an atmospheric pressure state, a reduced pressure state, or a pressurized state. Further, the above-described inert gas may be further supplied to the atmospheres of (B), (C), and (D).

  In the method according to the third aspect of the present invention, the lower limit value of the heat treatment temperature is 200 ° C. or higher, preferably 225 ° C. or higher, more preferably 250 ° C. or higher, and still more preferably 300 ° C. or higher. It is desirable. On the other hand, the upper limit value of the heat treatment temperature is set to 1200 ° C. or less, preferably 700 ° C. or less, more preferably 600 ° C. or less, still more preferably 500 ° C. or less, and still more preferably less than 400 ° C. desirable. By setting the upper limit value of the heat treatment temperature to 700 ° C. or less, it becomes difficult for the steepness of the interface in the superlattice structure to collapse due to diffusion of atoms (for example, In) constituting the nitride compound semiconductor layer. Further, by setting the upper limit of the heat treatment temperature to 600 ° C. or lower, further 500 ° C. or lower, and lower than 400 ° C., it is possible to more reliably prevent nitrogen atoms from separating from the nitride compound semiconductor layer. In addition, diffusion of p-type impurities such as Mg is more difficult to occur. Further, although depending on the heat treatment atmosphere, the surface of the nitride compound semiconductor layer is further hardly oxidized.

  In the method according to the first, second, or third aspect of the present invention, a hydrogen permeable film may be formed on the surface of the nitride compound semiconductor layer. . In this case, examples of the material constituting the hydrogen permeable membrane include a so-called hydrogen storage metal such as palladium (Pd) and a hydrogen storage alloy. The film thickness of the hydrogen permeable film may be any film thickness that can prevent the nitrogen atoms from separating from the nitride compound semiconductor layer by heat treatment. The hydrogen permeable film is formed by, for example, a physical vapor deposition method (PVD method) such as a sputtering method or a vacuum deposition method, or a chemical vapor deposition method (CVD method), depending on the constituent materials. be able to. For example, a hydrogen permeable film made of palladium (Pd) allows hydrogen gas to permeate at a high temperature, so that hydrogen atoms in the nitride compound semiconductor layer are released into the heat treatment atmosphere, and the surface of the nitride compound semiconductor layer is oxidized. Can be prevented. Furthermore, since palladium can be easily peeled off from the nitride compound semiconductor layer and can also be used as a p-side electrode, the semiconductor element is compared with the cap layer disclosed in Japanese Patent No. 2540791. No increase in the number of steps in the manufacturing process is caused.

  Specific examples of the nitride compound semiconductor layer in the present invention include GaN, AlGaN mixed crystal or AlInGaN mixed crystal, BAlInGaN mixed crystal, InGaN mixed crystal, InN, and AlN. It can be formed by vapor phase epitaxy (MOCVD) or molecular beam epitaxy (MBE). Examples of p-type impurities include Mg, Zn, Cd, Be, Ca, Ba, and O.

  Examples of semiconductor elements in the method of manufacturing a semiconductor element according to the first aspect, the second aspect, or the third aspect of the present invention include transistors such as a semiconductor laser (LD), a light emitting diode (LED), and an HBT. it can.

  The heat treatment can be performed using, for example, various heating devices such as a heating device using a heating gas such as an electric furnace or a hot air heating device, a light irradiation device such as infrared rays, ultraviolet rays, and microwave irradiation, and an electromagnetic wave irradiation device.

  In the method according to the first aspect of the present invention, the temperature of the heat treatment temperature is set to 200 ° C. or more and less than 400 ° C., which is lower than that of the prior art, and further, the heat treatment is performed for a longer time than before. Low resistance and activation can be achieved. In the method according to the second aspect of the present invention, the heat treatment is performed in a state where the heating temperature T and the heating time t are t ≧ 100 and the condition of the formula (1) is satisfied. The resistance and activation of the compound semiconductor layer can be reliably achieved. Furthermore, in the method according to the third aspect of the present invention, since the heat treatment is performed in an atmosphere containing oxygen gas or water vapor, the lower limit value of the heat treatment temperature is compared with that of the prior art. Can be reduced. Moreover, in the method according to the first aspect, the second aspect, or the third aspect of the present invention, in particular, the heating atmosphere is an atmospheric atmosphere or at least an atmosphere supplied with oxygen gas. The resistance and activation of the nitride compound semiconductor layer can be reduced in a short heat treatment time. This is because, for example, moisture contained in the air atmosphere acts as a kind of catalyst on the surface of the nitride compound semiconductor layer during heat treatment, or oxygen acts as a kind of catalyst, and the nitride compound semiconductor layer It is presumed that hydrogen desorption is promoted.

  In the method according to the first aspect of the present invention, the resistance of the nitride compound semiconductor layer can be reduced and activated by setting the heat treatment temperature lower than that of the prior art and further performing the heat treatment for a longer time than before. it can. In the method according to the second aspect of the present invention, the resistance and activation of the nitride compound semiconductor layer can be reliably achieved by defining the heating temperature T and the heating time t. Furthermore, in the method according to the third aspect of the present invention, since the heat treatment is performed in an atmosphere containing oxygen gas or water vapor, the lower limit value of the heat treatment temperature is compared with that of the prior art. Can be reduced. In addition, by setting the heat treatment temperature to less than 400 ° C., the decomposition pressure of the nitride compound semiconductor layer becomes substantially zero, so that nitrogen atoms can be reliably prevented from separating from the nitride compound semiconductor layer. . Further, since the heat treatment temperature can be made lower than that of the conventional one, diffusion of p-type impurities such as Mg is difficult to occur, or, moreover, the superheat due to the diffusion of atoms (for example, In) constituting the nitride compound semiconductor layer. It is difficult for the steepness of the interface in the lattice structure to collapse and, for example, the active layer of the semiconductor laser is hardly degraded, and a high-quality semiconductor laser can be manufactured. Furthermore, it is necessary to perform heat treatment for a longer time than in the past, but if the heat treatment temperature is less than 400 ° C., a large amount of treatment can be performed at one time, which can sufficiently cope with mass production of semiconductor elements. Furthermore, by setting the heat treatment temperature to less than 400 ° C., the surface of the nitride compound semiconductor layer is hardly oxidized, although it depends on the heat treatment atmosphere. When the p-side electrode is formed on the surface of the nitride compound semiconductor layer after heat-treating the nitride compound semiconductor layer, it is necessary to remove the oxide film on the surface of the nitride compound semiconductor layer. When the temperature is less than ° C, the oxide film formed on the surface of the nitride compound semiconductor layer can be easily removed.

  Hereinafter, the present invention will be described based on examples with reference to the drawings.

  Example 1 relates to a heat treatment method for a nitride compound semiconductor layer according to the first, second, and third aspects of the present invention. In Example 1, the heating atmosphere was an atmospheric atmosphere (pressure: atmospheric pressure).

  In Example 1, first, a buffer layer having a thickness of 40 nm is formed on a sapphire substrate, and a non-doped 1 μm-thick GaN layer containing no impurities is formed thereon. A 1 μm thick nitride compound semiconductor layer made of GaN doped with Mg as a p-type impurity was formed. Each of these layers was formed based on the MOCVD method. The sample thus obtained was cut into 5 mm squares, and electrodes made of palladium (Pd) having a thickness of 0.3 μm were formed at the four corners by vapor deposition to obtain samples for heat treatment evaluation.

  This heat treatment evaluation sample is placed on a stainless steel heating plate heated to TC (specifically, 385 ° C, 415 ° C, 485 ° C), and the stainless steel is placed on the heat treatment evaluation sample. The weight of the product was put on and the adhesion between the sample for heat treatment evaluation and the heating plate was improved. The heating atmosphere was an air atmosphere (average temperature 28 ° C., average relative humidity 68%). During the heat treatment, hydrogen was released from the heat treatment evaluation sample through a minute gap between the heating plate and the heat treatment evaluation sample.

  After a predetermined time, the sample for heat treatment evaluation was removed from the heating plate, and the electrical resistivity and Hall coefficient of the sample for heat treatment evaluation were measured based on the van der Pauw method. Thereafter, the heat treatment evaluation sample was again placed on the heating plate, and the heat treatment was continued.

  A heat treatment evaluation sample formed by forming a hydrogen permeable film made of palladium (Pd) having a thickness of 0.3 μm on a nitride compound semiconductor layer having a thickness of 1 μm made of GaN doped with Mg as a p-type impurity. The electrical resistivity and Hall coefficient were measured together. In this sample, a part of the hydrogen permeable film corresponding to the electrode was left and the other part of the hydrogen permeable film was removed by etching before the measurement of the electrical resistivity and the Hall coefficient.

  The electric resistivity at T = 385 ° C., 415 ° C., and 485 ° C., and the carrier concentration based on the Hall coefficient measurement results are shown in FIGS. 1 and 2, respectively. In the graph of FIG. 1, the horizontal axis is the square root of time t (unit: minute), and the vertical axis is the carrier concentration. In the graph of FIG. 2, the horizontal axis is the square root of time t (unit: minute), and the vertical axis is the electrical resistivity measurement result. In the graph of FIG. 1, the black square mark indicates the carrier concentration at T = 385 ° C., the white square mark indicates the carrier concentration at T = 415 ° C., and the white circle indicates the carrier concentration at T = 485 ° C. Show. Further, in the graph of FIG. 2, the black square mark indicates the electrical resistivity at T = 385 ° C., the white square mark indicates the electrical resistivity at T = 415 ° C., and the white circle indicates the electrical resistivity at T = 485 ° C. Resistivity is shown. Further, the black circle mark in FIG. 1 and the black circle mark in FIG. 2 are the carrier concentration and electrical resistivity at T = 385 ° C. in the heat treatment evaluation sample on which the hydrogen permeable film was formed, respectively. 1 and 2, it can be seen that even when the heat treatment temperature is less than 400 ° C., the carrier concentration increases and the electrical resistivity decreases as the heat treatment time increases. In addition, the measurement result in the heat treatment evaluation sample in which the hydrogen permeable film is formed is worse than the measurement result in the heat treatment evaluation sample in which the hydrogen permeable film is not formed. This is probably because the speed is slow.

  From the results shown in FIG. 1, it can be seen that the carrier concentration C is substantially proportional to the square root of the heat treatment time t. From this result, it is presumed that the increase in carrier concentration, that is, activation is progressing by diffusion, and it can be assumed that the following equation (2) is followed. Here, T is a heat treatment temperature (unit: K).

C = D ₀ · (√t) · exp [−α / T] (2)

Here, assuming that the carrier concentrations C ₁ , C ₂ , C ₃ at the heat treatment temperatures 385 ° C., 415 ° C., 485 ° C. are proportional to the square root of the heat treatment time t, the heat treatment temperatures 385 ° C., 415 ° C., The coefficients D ₁ , D ₂ and D ₃ at 485 ° C. were obtained.

C ₁ = D ₁ √ (t) (3-1)
C ₂ = D ₂ √ (t) (3-2)
C ₃ = D ₃ √ (t) (3-3)

as a result,
D ₁ = 1.39 × 10 ¹⁶
D ₂ = 3.61 × 10 ¹⁶
D ₃ = 1.17 × 10 ¹⁷
The result was obtained.

Based on this result, coefficients D ₀ and α were obtained from the following equation (4). Note that the values of D ₁ , D ₂ , and D ₃ described above were used as the value of D. As a result, coefficients ln (D ₀ ) = 53 and α = 1.04 × 10 ³ were obtained.

D = D ₀ exp [−α / T] (4)

  When Expression (2) is transformed, the following Expression (5) is obtained. Therefore, if the heat treatment temperature T on the left side is higher than the right side of Equation (5), a desired carrier concentration can be obtained after the heat treatment.

T = α / [ln (√t) + ln (D ₀ ) −ln (C)] (5)

In Formula (5), the graph when changing the carrier density C (unit: cm ^<-3> ) of the nitride compound semiconductor layer after heat processing is shown in FIG. In FIG. 3, the vertical axis represents the heat treatment temperature T (unit: ° C), and the horizontal axis represents the heat treatment time (unit: minutes). In FIG. 3, the black diamond mark is for C = 1 × 10 ¹⁶ cm ⁻³ , the black square mark is for C = 5 × 10 ¹⁶ cm ⁻³ , and the black triangle mark is for C = This is the case of 1 × 10 ¹⁷ cm ⁻³ , “×” marks are for C = 3 × 10 ¹⁷ cm ⁻³ , and “*” marks are for C = 5 × 10 ¹⁷ cm ⁻³ . Yes, black circles are for C = 1 × 10 ¹⁸ cm ⁻³ .

  From FIG. 3 and formula (5), for example, the relationship between the heat treatment time t when the heat treatment temperature is 400 ° C. and 385 ° C. and the carrier density C of the nitride compound semiconductor layer after the heat treatment is shown in Table 1 below. And in Table 2. The heat treatment time of 41 hours or 82 hours is a time that does not cause a problem in the manufacture of the semiconductor element.

[Table 1]
Heat treatment temperature T = 400 ° C
Carrier density C (cm ⁻³ ) Heat treatment time t (hours)
3 × 10 ¹⁷ 3.7
5 × 10 ¹⁷ 10
1 × 10 ¹⁸ 41

[Table 2]
Heat treatment temperature T = 385 ° C
Carrier density C (cm ⁻³ ) Heat treatment time t (hours)
3 × 10 ¹⁷ 7.4
5 × 10 ¹⁷ 21
1 × 10 ¹⁸ 82

  The heat treatment atmosphere is an atmosphere supplied with oxygen gas, an atmosphere supplied with oxygen gas and hydrogen gas, an atmosphere supplied with oxygen gas and water vapor, oxygen gas, hydrogen gas and water vapor supplied from the air atmosphere. The same test was performed in an atmosphere, an inert gas atmosphere, an inert gas atmosphere containing water vapor, a reduced pressure atmosphere, and a reduced pressure atmosphere containing water vapor, but the same tendency as in the air atmosphere was obtained.

  Example 2 relates to a method of manufacturing a semiconductor device including a semiconductor laser. Hereinafter, an outline of a manufacturing method based on a pressurized MOCVD method which is a kind of vapor phase growth method will be described. In the pressurized MOCVD method, the pressure in the MOCVD apparatus when forming various compound semiconductor layers is 1.1 atm to 2.0 atm, preferably 1.2 atm to 1.8 atm. Is desirable. In this way, by adopting the pressurized MOCVD method, it is possible to reliably prevent the occurrence of a phenomenon in which nitrogen is desorbed during the growth of the compound semiconductor layer and the compound semiconductor layer becomes deficient in nitrogen. In the following description, the pressure in the MOCVD apparatus when forming various compound semiconductor layers was set to 1.2 atmospheres. The pressure in the MOCVD apparatus may be a normal pressure. Further, the film forming temperature of various compound semiconductor layers other than the buffer layer and the active layer is set to about 1000 ° C., and the film forming temperature of the active layer is set to 700 to 800 ° C. to suppress the decomposition of In. The film forming temperature was set to about 560 ° C.

  First, for example, the sapphire substrate 10 is carried into an MOCVD apparatus (not shown), the MOCVD apparatus is evacuated, and then the sapphire substrate 10 is heated while flowing hydrogen gas to remove oxide on the surface of the sapphire substrate 10. . Next, the buffer layer 11 made of GaN is formed on the sapphire substrate 10 based on the MOCVD method. In forming each layer, trimethylgallium (TMG) gas may be used as the Ga source and ammonia gas may be used as the N source.

Thereafter, for example, the n-side contact layer 12 made of an n-type GaN layer to which silicon (Si) is added as an n-type impurity, and the n-type cladding layer made of an n-type AlGaN mixed crystal layer to which silicon (Si) is added as an n-type impurity. 13. An n-type guide layer 14 composed of an n-type GaN layer to which silicon (Si) is added as an n-type impurity is sequentially grown. Monosilane gas (SiH ₄ gas) may be used as the Si source, and trimethylaluminum (TMA) gas may be used as the Al source.

Subsequently, an active layer 15 having a multiple quantum well structure in which mixed crystal layers of Ga _x In _1-x N (where X ≧ 0) having different compositions are stacked on the n-type guide layer 14 is formed. Trimethylindium (TMI) gas may be used as the In source.

  After the active layer 15 is grown, a p-type guide layer 16 made of p-type GaN to which magnesium (Mg) is added as a p-type impurity and a p-type to which magnesium (Mg) is added as a p-type impurity are formed on the active layer 15. A p-type cladding layer 17 made of an AlGaN mixed crystal layer and a p-side contact layer 18 made of a p-type GaN layer to which magnesium (Mg) is added as a p-type impurity are successively grown. Note that cyclopentadienyl magnesium gas may be used as the Mg source.

  Thereafter, heat treatment is performed in a manner substantially similar to that described in Example 1, for example, using a hot air drying apparatus. The heat treatment atmosphere was air, the heat treatment temperature was 385 ° C., and the heat treatment time was 84 hours (3.5 days). As a result, the p-type impurities contained in the p-type guide layer 16, the p-type cladding layer 17, and the p-side contact layer 18 are activated, and the electrical resistivity of each of these layers can be reduced.

  Next, a resist layer is formed on the p-side contact layer 18 so that the p-side contact layer 18 above the position where the n-side electrode 20 is to be formed, and the p-side contact is formed using the resist layer as an etching mask. The layer 18, the p-type cladding layer 17, the p-type guide layer 16, the active layer 15, the n-type guide layer 14, and the n-type cladding layer 13 are selectively removed to expose the n-side contact layer 12. Next, the resist layer is removed, and, for example, a platinum (Pt) layer and a gold (Au) layer are sequentially deposited on the exposed p-side contact layer 18 to form a p-side electrode 19. Further, on the exposed n-side contact layer 12, for example, a titanium (Ti) layer, an aluminum (Al) layer, a platinum layer, and a gold layer are sequentially deposited to form the n-side electrode 20. Thereafter, heat treatment is performed to alloy the n-side electrode 20. Thus, a semiconductor laser having a schematic cross-sectional view shown in FIG. 4 can be completed.

  As mentioned above, although this invention was demonstrated based on the preferable Example, this invention is not limited to these. The conditions, various numerical values, materials used and the like described in the examples are examples and can be appropriately changed. The formation of each layer made of a nitride compound semiconductor is not limited to the MOCVD method, but can also be performed by an MBE method, a hydride vapor phase growth method in which halogen contributes to transport or reaction, and the like. In addition to the sapphire substrate, a GaN substrate or SiC substrate can be used as the substrate. In the embodiments, a semiconductor laser is used as the semiconductor element. However, the semiconductor element manufacturing method of the present invention can be applied to a light emitting diode (LED) or a transistor such as an HBT.

It is a graph which shows the carrier density | concentration based on the Hall coefficient measurement result in heat processing temperature T = 385 degreeC, 415 degreeC, and 485 degreeC. It is a graph which shows the electrical resistivity in heat processing temperature T = 385 degreeC, 415 degreeC, and 485 degreeC. It is a graph which shows the relationship between the heat processing temperature T and the heat processing time t when changing the carrier density C of the nitride compound semiconductor layer after heat processing. It is typical sectional drawing of a semiconductor laser.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Sapphire substrate, 11 ... Buffer layer, 12 ... N-side contact layer, 13 ... N-type cladding layer, 14 ... N-type guide layer, 15 ... Active layer, 16. .... p-type guide layer, 17 ... p-type cladding layer, 18 ... p-side contact layer, 19 ... p-side electrode, 20 ... n-side electrode

Claims (6)

A nitride compound semiconductor layer to which a p-type impurity is added,
(A) Atmosphere,
(B) an atmosphere supplied with oxygen gas and hydrogen gas;
(C) an atmosphere supplied with oxygen gas and water vapor;
(D) an atmosphere supplied with oxygen gas, hydrogen gas, and water vapor;
(E) an inert gas atmosphere containing water vapor, and
(F) a reduced-pressure atmosphere containing water vapor,
A method for heat-treating a nitride compound semiconductor layer, comprising heating at a temperature of 200 ° C. or higher and 1200 ° C. or lower in an atmosphere of any one of the above.   The method for heat-treating a nitride compound semiconductor layer according to claim 1, wherein heating is performed at a temperature of 200 ° C or higher and lower than 400 ° C.   The method for heat treatment of a nitride compound semiconductor layer according to claim 1, wherein a hydrogen permeable film is formed on a surface of the nitride compound semiconductor layer. A nitride compound semiconductor layer to which a p-type impurity is added,
(A) Atmosphere,
(B) an atmosphere supplied with oxygen gas and hydrogen gas;
(C) an atmosphere supplied with oxygen gas and water vapor;
(D) an atmosphere supplied with oxygen gas, hydrogen gas, and water vapor;
(E) an inert gas atmosphere containing water vapor, and
(F) a reduced-pressure atmosphere containing water vapor,
A method of manufacturing a semiconductor device, comprising a step of heating at a temperature of 200 ° C. or higher and 1200 ° C. or lower in any one of the atmospheres.   5. The method of manufacturing a semiconductor device according to claim 4, wherein heating is performed at a temperature of 200 ° C. or higher and lower than 400 ° C.   6. The method of manufacturing a semiconductor device according to claim 4, wherein a hydrogen permeable film is formed on a surface of the nitride compound semiconductor layer.

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