KR20050025054A - AlGaInN based P-N Diode and Fabrication Method thereof - Google Patents

Abstract

PURPOSE: An AlGaInN based p-n diode and a method for fabricating the same are provided to obtain a p-type AlGaInN only by growing of a thin film without the post activation annealing using a hydrazine family source capable of absorbing hydrogen in the thermal decomposition. CONSTITUTION: A V-family nitrogen precursor includes a hydrazine family source creating a radical capable of combining hydrogen radicals in the thermal decomposition. The hydrogen radicals separated from NH3 is removed, and then a P-Al(x)Ga(y)In(z)N layer is grown.

Description

Aluminum gallium indium nitride based P-N diode device and manufacturing method thereof {AlGaInN based P-N Diode and Fabrication Method about}

The present invention relates to an AlGaInN-based PN diode device by a novel P-type AlGaInN: Mg growth method, and a method for manufacturing the same. The present invention relates to an AlGaInN-based PN diode device using a hydrazine-based source having a hydrogen adsorption function grown by MOCVD (Metal Organic Chemical Vapor Deposition), and a method of manufacturing the same.

In general, the epi structure of a conventional AlGaInN-based PN diode light emitting device, as shown in Figure 1, the buffer layer 11, the N-type GaN layer 12, the N-type AlGaN on the upper side of the sapphire substrate 10, which is an insulating substrate After crystal growth of the cladding layer 13, the InGaN (or GaN) active layer 14, the P-type AlGaN layer 15, and the P-type GaN layer 16 in sequence, it is transparent on the P-type GaN layer 16 The electrode 17 is formed to form a P-type metal electrode 18 thereon, and the N electrode 19 is formed on the N-GaN layer. If necessary, the N layer can be composed of AlGaInN single or multiple layers, and the P layer can also be composed of AlGaInN single or multiple layers is a natural fact in the existing AlGaInN-based light emitting device.

In the commercial light emitting device as described above, MOCVD (Metal Organic Chemical Vapor Deposition), which is one of vapor deposition methods, is mainly used.

In this case, as shown in Figure 2a, ammonia (NH ₃ ) is used as the nitrogen precursor, the growth of GaN is H ₂ , N ₂ is used as the carrier gas for InGaN.

At this time, the ammonia (NH ₃ ) is very thermally stable, only a few% of NH ₃ is pyrolyzed even at 1000 ° C. or higher, contributing to the growth of GaN as a nitrogen source.

Therefore, high temperature growth is inevitable and the V / III fraction for good crystallinity GaN growth is also very high in order to increase the pyrolysis efficiency, and generally uses a high V / III fraction of about 4000 to 10,000.

As shown in the equation below, a large amount of ammonia used for GaN growth releases a large amount of hydrogen as a by-product, and in addition to H ₂ used as a carrier gas, may provide a cause of Mg-H passivation. do.

NH ₃ ----------> N + H + H ₂

           Pyrolysis Nitrogen Group Hydrogen Group Hydrogen

That is, when the ammonia gas is pyrolyzed at high temperature, when the nitrogen group (N), the hydrogen group (H), and the hydrogen (H ₂ ) are formed, the hydrogen group formed easily combines with the Mg during the growth of the AlGaInN: Mg thin film, thereby suppressing the Mg. Mg-H bonds are formed by binding not to act as a acceptor.

Accordingly, the AlGaInN: Mg thin film layer in which a large amount of Mg-H bond is formed does not form a P-type, but rather forms an N-type thin film having a very high resistivity.

This phenomenon is already very well known in the conventional P-type GaN-based thin film growth, and many studies have been published through several paths.

As described above, when P-type AlGaInN: Mg is grown using ammonia (NH ₃ ), Mg, a P-type dopant, forms an Mg-H bond with hydrogen to passivate Mg, an impurity, and thus has a very high resistance. In order to convert the AlGaInN: Mg thin film layer into a P-type semiconductor, it is converted into a P-type by performing post-activation annealing.

As described above, the most commonly used method of post-heat treatment method of converting to P-type is a method of heat-treating a nitrogen carrier at a high temperature of 400 ° C. or more for a predetermined time and irradiating an electron beam to the AlGaInN: Mg layer to form a P-type. The method of obtaining this is being used.

The post-heat treatment method is a method of giving a constant energy to hydrogen and magnesium bonds to break the bonds to diffuse and extract hydrogen groups out of the thin film. The principle is the same.

And, as described above, the principle of obtaining the P-type by post-heat treatment is as shown in Figure 2b, using a conventional ammonia, gallium source and magnesium source to grow a P-GaN layer, When the growth is completed, an N-type layer close to the insulator is formed by the Mg-H bond, and when the heat treatment or the electron beam is irradiated, the hydrogen group is removed to obtain the P-type.

However, in the AlGaInN: Mg thin film growth using the conventional ammonia as described above, the P-type can be obtained only after the post-heat treatment such as thin film growth, and the post-heat treatment process as described above In addition to increasing the complexity of the product, as well as damage to the active layer can lead to product defects.

Therefore, a method of obtaining an as-grown P-type GaN layer at the same time as the aforementioned growth without the need for post-heat treatment has been disclosed in some academic papers. There is a method using nitrogen as a gas. In this case, since ammonia, which generates a large amount of hydrogen, is used as a nitrogen precursor, there is a problem in the reproducibility in the method of obtaining as-grown P-type due to fundamental hydrogen blocking. In addition, the invention proposed by Sony Corporation (US6,043,140, US6,413,312 B1) uses a nitrogen precursor and a nitrogen carrier that do not generate hydrogen to fundamentally block the inflow of hydrogen during P-GaN growth to obtain as-grown P-type. The method is essentially the preferred method. However, we have grown the P-GaN by using Hydrazine as the nitrogen precursor and nitrogen as the carrier gas following the method suggested by Sony at the headquarters.The surface morphology of the P-GaN layer applicable to GaN LED devices. Failed to obtain Surface Morphology. According to a published paper, it is known that there is still considerable difficulty in obtaining high quality when growing GaN using a hydrazine nitrogen precursor. Therefore, the method proposed by Sony may be a reasonable approach in principle, but it is considered to be a difficult technique in terms of performance, especially in terms of mass production of commercial light emitting devices. Moreover, the cost of Hydrazine-based sources is incomparably higher than that of ammonia. Therefore, according to the method proposed by Sony, when hundreds of times of Hydrazine is used in comparison with the amount of gallium, Cost competitiveness will likely be lost.

An object of the present invention for solving the above disadvantages, to minimize the hydrogen passivation of Mg impurities by hydrogen during the growth of P-AlGaInN: Mg to simultaneously grow the thin film and P-type without a separate post-heat treatment process To provide an AlGaInN-based PN diode device using a hydrazine-based source having a hydrogen adsorption function to obtain a and a method of manufacturing the same.

To this end, the main feature of the present invention is to use a principle of minimizing Mg-H bond formation by using a hydrazine-based source having hydrogen adsorption function mixed with an ammonia nitrogen precursor during pyrolysis. The principle explanation for this is explained in detail in the configuration of the invention.

In order to achieve the above object, AlGaInN system comprising the step of growing a P-Al (x) Ga (y) In (y) N layer (x + y + z = 1) using NH 3 as a Group V nitrogen precursor In the method of manufacturing a PN diode device, the growth of the P-Al (x) Ga (y) In (z) N layer in this step is a hydrazine system that generates radicals capable of bonding with a hydrogen group upon thermal decomposition with NH 3 as a nitrogen precursor. Provided is a method of manufacturing an AlGaInN-based PN diode device, wherein the hydrogen group separated from NH 3 by using a source is combined with the radical to be removed.

In addition, the present invention provides an AlGaInN-based PN diode device comprising a P-Al (x) Ga (y) In (y) N layer (x + y + z = 1) grown using NH3 as a Group V nitrogen precursor. The group V nitrogen precursor further includes a hydrazine-based source that generates radicals capable of bonding with a hydrogen group during pyrolysis, and the P-Al (x) Ga (y) In (z) N layer is hydrogen separated from NH3. An AlGaInN-based PN diode device is provided which is grown by allowing groups to be removed in combination with the radicals.

The present invention also provides a substrate, a buffer layer grown on the substrate, an N-Al (a) Ga (b) In (c) N layer (a + b + c = 1), N-Al (a) Ga ( b) Active layer grown on In (c) N layer, P-Al (x) Ga (y) In (z) N layer (x + y + z = 1), N-Al (a) Ga grown on active layer (b) an AlGaInN-based PN diode comprising an N-type electrode in electrical contact with the In (c) N layer and a P-type electrode in electrical contact with the P-Al (x) Ga (y) In (z) N layer. In the device, the P-Al (x) Ga (y) In (z) N layer is a nitrogen precursor separated from NH3 using ammonia and a hydrazine-based source that generates radicals capable of bonding with hydrogen groups during pyrolysis. There is provided an AlGaInN-based PN diode device which is obtained by allowing a hydrogen group to be combined with the radical to be removed.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

As shown in FIG. 3, a Mg-H complex (Hydrazine) -based source having hydrogen adsorption function during pyrolysis was mixed with an ammonia nitrogen precursor (Nitrogen Precursor) to form an Mg-H complex due to hydrogen groups in an AlGaInN: Mg thin film. Formation is suppressed to obtain P-form without thin film growth and post-heat treatment process.

At this time, H group in the grown AlGaInN: Mg thin film can be minimized.

And, when using a hydrazine (Hydrazine) source having a hydrogen adsorption function and mixed with an ammonia nitrogen precursor will be described the principle that can be obtained P-type AlGaInN: Mg without the post-heat treatment process.

Herein, dimethylhydrazine (DM-hydrazine) is used as an example of a hydrazine-based source used as a hydrogen adsorption function. The binding energy between the nitrogen and nitrogen groups of this material is 33.4Kcal, which is much lower than 93.3Kcal, the binding energy between the nitrogen and hydrogen groups of ammonia.

Therefore, even at low temperatures of 500 ° C. or more, the nitrogen-to-nitrogen bond of the hydrazine material is easily broken to form NH ₂ groups.

As an example, a dimethyl hydrazine (DM-hydrazine) such as Scheme 2 is described as an example.

(CH ₃ ) ₂ N-NH ₂ --------------------> (CH ₃ ) ₂ N + NH ₂

                  pyrolysis

In this case, the formed NH ₂ group is a very unstable and highly reactive substance, which is intended to be converted into a thermally stable ammonia (NH ₃ ) form by combining with surrounding H groups as soon as possible, and the (CH ₃ ) 2N group formed primarily by pyrolysis of hydrazine. Through the second pyrolysis, N and CH ₃ groups are formed, and CH _{3 is} also thermally unstable to combine with surrounding hydrogen to form CH ₄ .

Therefore, when hydrazine is used as a nitrogen precursor for AlGaInN: Mg growth as described above, the effect of lowering the concentration of hydrogen groups present in the gas phase layer as in Scheme 3 is generated. It can minimize or eliminate the formation of easily occurring Mg-H complexes.

(CH ₃ ) ₂ N ----------> 2 (CH ₃ ) + N ---------> 2CH ₄ + N

Pyrolysis hydrogen group (H) bond

NH ₂ ----------> NH ₃

Hydrogen group (H) bond

As a result, hydrogen concentration lowering radicals (NH ₂ , CH ₃ ) are generated from hydrazine as described in Scheme 3, thereby lowering the concentration of hydrogen present in the reactor, thus forming Mg-H composites during thin film growth. It minimizes itself, so that the P-GaN crystal itself can be formed into a P-type.

Then, the x, y, z ratio of Al (x) Ga (y) In (z) N as described above (x + y + z = 1, 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, 0 ≤ z 1) to form a p-Al (x) Ga (y) In (z) N: Mg layer.

In addition, a thin film layer of an optical device such as an Al (x) Ga (y) In (z) N-based light emitting diode (LED), a laser diode (LD), and a photodiode (PD) may be used as a P-type Al (x) Ga (y) It is formed of an In (z) N: Mg thin film layer.

In addition, a thin film layer of an Al (x) Ga (y) In (z) N-based electronic device is formed of a P-type Al (x) Ga (y) In (z) N: Mg thin film layer.

The above theoretical principles were clearly demonstrated through several experiments, and the experimental results are described below.

In this experiment, dimethylhydrazine (DMHy) was used as a hydrazine source, trimethylgallium (TMGa) as a gallium (Ga) source, and Cp ₂ Mg as a magnesium (Mg) source. .

In addition, ammonia was used as a main nitrogen precursor, and hydrazine was mixed and used to remove the hydrogen group. When hydrazine is used, the NH ₂ and CH ₃ groups also reduce the concentration of hydrogen groups, but also serve to generate nitrogen groups. Therefore, when using hydrazine, there is an advantage in that the use of ammonia may be used in a smaller amount.

In addition, the amount of hydrazine used in the growth of the P-type AlGaInN: Mg thin film is preferably a molar ratio of hydrazine and gallium (V (hydrazine) / III (gallium)) of 1 or more and 500 or less, More preferably, 1 or more and 300 or less are used.

If less than 1 is used, the relative amount of hydrazine relative to ammonia is small, which is insufficient to reduce the hydrogen concentration compared to hydrogen formation by ammonia decomposition. In addition, the use of excessive Hydrazine of more than 500 may deteriorate the characteristics of the thin film due to the amount of C-N groups generated in the by-products caused by Hydrazine. Even if 10 is used in this experiment, the role of lowering the hydrogen concentration is sufficient, so even if considering the amount of ammonia used in some cases, it is difficult to obtain more improved results using the amount of 300 or more. desirable.

At this time, the molar fraction of V (ammonia) / III (Ga) is preferably 100 or more and 10,000 or less, more preferably 100 or more and 8000 or less.

If less than 100 is used, although the nitrogen precursor is formed in hydrazine, the quality of the thin film is extremely poor due to the nitrogen deficiency due to the small amount of undesired nitrogen precursor. Therefore, in consideration of thermal decomposition of ammonia, it is preferable to use more than 100. If the amount of ammonia is used more than 10,000, the amount of hydrogen produced by ammonia increases, so that the possibility of forming a bond between magnesium and hydrogen is relatively high. Therefore, it is judged that it is preferable to use the existing ammonia condition below 8000. However, although more than 10,000 ammonia may be used, in this case, as the hydrogen bonds become larger, the electrical characteristics of the device tend to increase compared with the conventional post-heat treatment. Therefore, the present invention is intended to obtain as low electrical properties as possible compared to the existing heat treatment process, but 8,000 or more are excluded from the claims, it is determined that a little higher than 10000 ammonia can be used if a slightly higher electrical properties than conventional.

In addition, Figure 5a is a surface photo of the P-type GaN grown when a mixture of ammonia and hydrazine (V / III = 10) as a surface photograph of the sample is very excellent in morphology (morphology).

And, the surface photograph of the sample by the comparative experiment is for the case of using only the hydrazine in the same amount as the nitrogen precursor, as shown in Figure 5b, which is a thin film formed properly when the amount of hydrazine used in the experiment It can be seen that it is not. In addition, it can be seen that the thin film is not uniformly grown and is partially irregularly formed in an island shape. Therefore, as mentioned above, the main purpose of the hydrazine in the present invention is to form a hydrogen-lowering radical. However, of course, the nitrogen resulting from the pyrolysis of hydrazine can help the nitrogen precursors in the growth of GaN thin film.

Subsequently, hydrogen (H ₂ ) together with nitrogen (N ₂ ) is used as a carrier gas used in the growth of the P-type AlGaInN: Mg thin film proposed in the present invention. It is preferable to mainly use a nitrogen group, but when using a mixture of hydrogen can obtain a higher hole concentration (Hole Concentration).

This is because hydrogen plays a role in lowering the underlying impurity concentration during the growth of GaN. Therefore, according to the present invention, when growing P-type AlGaInN: Mg thin film, nitrogen, hydrogen or a mixed gas of nitrogen and hydrogen may be used as a carrier gas.

The reason why the base impurity concentration can be lowered by mixing the hydrogen carrier is that the hydrogen carrier removes the C-N group generated from the hydrazine. Therefore, it is considered that the base concentration is reduced by reducing the adsorption of the C-N group in the P-GaN.

The P-type GaN thin film was grown using the method proposed in the present invention, and Hall and photoluminescence (PL) were measured and compared with the conventional P-type GaN layer using only ammonia.

As shown in FIG. 6, after forming a buffer on the sapphire substrate and then forming a non-doped GaN layer thereon, a P-type GaN layer was grown using ammonia, hydrazine, TMGa and Cp ₂ Mg. As a comparative sample, a P-GaN layer having the same structure was grown and compared using ammonia, TMGa, and Cp ₂ Mg.

In addition, since the P-GaN layer using ammonia has the same characteristics as an insulator due to Mg-H bonding, it is impossible to measure the hole. The hole measurement was performed after conversion to the -shape.

On the contrary, P-GaN using hydrazine with hydrogen group adsorption function proposed in the present invention performs P and Ga without any heat treatment after thin film growth, and performs P-GaN without post-heat treatment process with thin film growth proposed in the present invention. Proved to be -type.

In addition, the P-type contact metal used in the hole measurement is measured without conducting contact metal-Alloy, so there is no controversy about the conversion to P-type due to the alloy heat treatment. Was removed beforehand.

In the case of using the proposed method of the present invention, the hole concentration is 2-13 x 10 ¹⁷ [/ cm ³ ] and the hole mobility is 10-50 [cm ² / Vs] without a post-process such as heat treatment. Got.

In addition, sheet resistance was obtained two to three times lower than the sample subjected to heat treatment using ammonia.

These measurement results are important supporting evidence of the invention that the hydrazine proposed by the present invention results in thin film growth and P-type AlGaInN: Mg thin film formation.

7A is a result of photoluminescence (PL) measurement of samples grown by the present invention, and FIG. 7B is a PL measurement result of P-GaN grown using ammonia, and P-GaN grown using ammonia in general. The PL characteristic of the tendency is that yellow bands tend to be largely measured above 500 nm with the presence of the PL spectra peak center between 430 and 450 nm.

However, when annealing P-GaN using only ammonia at high temperature (Activation Annealing), yellow bands of 500 nm or more are reduced, and yellow bands are almost eliminated when the heat treatment proceeds sufficiently, and this phenomenon is a common phenomenon.

On the other hand, in the P-GaN according to the proposal of the present invention as shown in Figure 7a was not measured yellow band (Yellow Band), PL results similar to the case of sufficiently heat treatment of P-GaN using ammonia, which is It is very different from the PL characteristics of conventional P-GaN.

In other words, P-GaN using a hydrazine-based source mixed with ammonia is considered to exemplify a significant difference from the conventional method using only NH3 nitrogen precursor.

LED was fabricated using the P-GaN formation method proposed in the present invention and analyzed.

Using the general phenomenon in LED growth using only ammonia, it is verified that the method proposed in the present invention is P-formed at the same time as the growth of a thin film, unlike the conventional P-GaN using only ammonia.

In the conventional LED device as shown in Figure 1, as shown in Table 1, after the high temperature after-heat treatment (Activation Annealing) that is commonly used to manufacture the device, the LED device according to the present invention The device was fabricated without hot post-heat treatment.

In addition, the LED sample taken out of the MOCVD reactor was subjected to an indium contact test in which an indium dot was attached to the surface to form a metal contact to measure the characteristics of the LED.

The basic reason is to completely block the unintentional heat treatment effect that may occur during the normal LED device fabrication process and to easily confirm the formation of the P-N diode.

In addition, the reactor was cooled to 300 ° C. at a growth temperature in an (ammonia + nitrogen) or (ammonia + hydrogen) atmosphere in order to prevent heat treatment effect (Activation) from occurring during the lowering of the reactor temperature after the growth of the LED in MOCVD.

It is known that the heat treatment effect is lost when the temperature of the reactor is reduced by using ammonia.

As described in Table 1, for P-GaN-grown LEDs using hydrazine, both reactors were cooled to 300 ° C under (ammonia + nitrogen) or (ammonia + hydrogen) atmospheres. It worked.

Therefore, because the conditions that the heat treatment effect (Activation) can not occur during the cooling of the reactor was used, these results are important experimental results to support the claim that the P- form with the growth of P-GaN.

In order to more clearly prove that P-type was formed with P-GaN growth, samples cooled in (ammonia + hydrogen) atmosphere were subjected to 850 ° C in (ammonia + hydrogen (10 liter) atmosphere). Annealing was performed for 10 minutes.

This is known to be a common fact. After annealing, P-form samples are reheated in an atmosphere above 500 ° C (ammonia + hydrogen) to form Mg-H composites again. This is to test the P-GaN formed by the method proposed in the present invention in order to disprove the experimental fact that the return to the same characteristics.

Experimental results are also shown in Table 1, unlike the conventional general fact that the LED having a P-GaN structure using the method proposed in the present invention almost maintained the electrical characteristics or emission characteristics in the indium contact test.

This means that the P-type was kept intact, and this experimental result is an important result supporting that the P-type growth principle proposed in the present invention is fundamentally different from the existing growth principle.

8 is a forward current-voltage curve measured on an LED chip fabricated according to a normal LED process procedure of a P-GaN-grown LED according to the present invention. Therefore, it has been experimentally proved that the LED grown according to the present invention can obtain the characteristics inferior to the existing LED without the post-heat treatment process.

In order to achieve the above object, the present invention provides the use of a mixed Group V precursor of a hydrazine-based source and ammonia (NH ₃ ) during the growth of P-type AlGaInN: Mg.

At this time, nitrogen or a mixed carrier of nitrogen and hydrogen may be used as the carrier gas.

Examples of hydrazine-based sources include dimethylhydrazine, tertiarybutilhydrazine, and monomethylhydrazine, but among them, dimethyl, which generates NH ₂ and CH ₃ groups simultaneously during pyrolysis. It is more preferable to use hydrazine (Dimethylhydrazine) according to the object of the present invention.

Example 1

An appropriate buffer layer 11 and an N-AlGaInN layer are grown on the substrate 10 by the MOCVD deposition method using NH ₃ , group III metal (Ga, In, Al) precursor as a group V nitrogen precursor, and metal organic material as a carrier gas and H ₂ as a carrier gas. After that, the carrier gas is changed to N ₂ to grow an AlGaInN-based active layer (multilayer or single layer) 14.

It is characterized by growing a P-AlGaInN layer by using a mixture of ammonia and hydrazine-based source as the main nitrogen precursor, and using N ₂ as a carrier gas.

The amount of hydrazine used for the growth of the P-type AlGaInN: Mg thin film is preferably a molar ratio of hydrazine and gallium (V (hydrazine) / III (gallium)) of 1 or more and 500 or less, more preferably. It is preferable to set it as 1 or more and 300 or less.

At this time, the amount of ammonia to be mixed is preferably in the V (ammonia) / III (Ga) fraction of 100 or more and 10000 or less, more preferably 100 or more and 8000 or less.

The main reason for using hydride-based sources is to thermally decompose at high temperatures to form hydrogen-lowering radicals, and additionally, pyrolyzed hydrazine may serve as a nitrogen precursor.

Example 2

As in Example 1, when hydrazine and ammonia are mixed to grow P-AlGaInN, nitrogen or hydrogen or nitrogen and hydrogen may be used as a carrier gas.

Example 3

When growing P-GaN by mixing hydrazine and ammonia as in Example 1, the growth temperature can be grown in the range of 500 ° C or more and 1150 ° C or less, and more preferably 700 ° C or more and 1100 ° C or less. desirable.

The temperature and temperature below 700 degrees deteriorate the characteristics and surface state of the grown P-GaN thin film, and when the high temperature is used above 1100 degrees, the active layer grown at a relatively low temperature is damaged.

Example 4

When P-GaN is grown by mixing hydrazine and ammonia as in Example 1, the growth pressure may be 1 tortor or more and 800torr or less, and more preferably 20 tortoror or less.

In the case of organometallic chemical vapor deposition (MOCVD), the reproducibility and stability of the equipment tend to be lower than 20torr and above 760torr due to the characteristics of the equipment.In particular, as the pressure increases, the pre-reaction of hydrazine increases, so it is used below 760torr. It is desirable to. As the premature reaction increases, the growth rate of the thin film decreases, and it becomes difficult to obtain the p-type at the same time as the thin film grows.

Example 5

After growing P-type P-GaN by the method proposed by the present invention, P-type can be obtained by cooling the reactor in ammonia and hydrogen atmosphere.

Example 6

After the P-type P-GaN is grown by the method proposed by the present invention, the P-type can be obtained by cooling the reactor in an ammonia and nitrogen atmosphere.

Example 7

After the P-type P-GaN is grown by the method proposed by the present invention, the P-type can be obtained by cooling the reactor in an ammonia, nitrogen, and hydrogen atmosphere.

Example 8

When the P-type AlGaInN layer is formed by the method proposed by the present invention, a single layer may be formed by forming a thickness of 10 angstroms or more and 10000 angstroms or less.

In consideration of sufficient hole supply, it is desirable to form a thickness of 10 angstroms or more, and when forming a thickness of 10000 angstroms or more, the device growth time is longer and the time for the active layer to be released at a high temperature increases the chance of damage to the active layer. do.

Example 9

When the P-Al (x) Ga (y) In (z) N layer is formed by the method proposed by the present invention, two or more layers of P-Al (x) Ga (y having different (x, y, z) values are different. In (z) N layers may be formed by lamination, and the thickness of each layer may be 10 angstroms or more and 10000 angstroms or less, and the sum of the thicknesses of the multilayers may be 10 angstroms. Iii) preferably at least 10000 Angstroms. In consideration of sufficient hole supply, it is preferable to form a thickness of 10 angstroms or more, and when forming a thickness of 10000 angstroms or more, the device growth time becomes longer and the time for the active layer to be released at a high temperature increases the possibility of damaging the active layer. Will be higher.

According to the present invention, when an AlGaInN-based PN diode is grown by MOCVD, P-AlGaInN: Mg is used by using a hydrazine source and a gas mixed with nitrogen or nitrogen and hydrogen as ammonia (NH ₃ ) and carrier gas. Hydrogen Passivation of Mg dopant by hydrogen can be minimized during growth, and As Grown P Type can be obtained simultaneously with thin film growth without Post Activation Annealing process.

While the invention has been shown and described with respect to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit or scope of the invention as provided by the following claims. I would like to clarify that those who have knowledge of this can easily know.

1 is a cross-sectional view showing an AlGaInN-based LED structure using a conventional insulating substrate.

FIG. 2A is an explanatory diagram of a source injection method in a metal organic chemical vapor deposition (MOCVD) for manufacturing a conventional LED.

2B is an explanatory diagram of a conventional growth method of P-GaN and a method of obtaining a P-type.

Figure 3 is an explanatory view of the source injection method in the metal organic deposition for manufacturing LED according to the present invention.

4 is an explanatory diagram illustrating a method of growing P-GaN and a method of obtaining a P-type in manufacturing an LED according to the present invention.

5A and 5B show a surface photograph of P-GaN and a comparison thereof when ammonia is used as a main nitrogen precursor and a hydrazine-based source is used for hydrogen adsorption function. This is a surface photograph of P-GaN that appears when only the same amount of hydrazine (Hydrazine) is used as the nitrogen precursor.

6 is a cross-sectional view of the structure of a specimen for measuring the Hall (Hall).

7A and 7B show photoluminescence (PL) measurement results of P-GaN and a comparison of P-GaN using conventional ammonia for comparison when hydrazine and ammonia mixed nitrogen precursors proposed in the present invention are used, respectively. PL measurement result diagram.

8 is a graph of a forward current-voltage curve measured by fabricating an LED after growing P-GaN of the LED according to the present invention.

<Description of Symbols for Main Parts of Drawings>

10 ... substrate 11 ... buffer layer

12 ... N type GaN layer 13 ... N type AlGaN cladding layer

14 ... InGaN active layer 15 ... P type AlGaN layer

16 ... P type GaN layer 17 ... transparent electrode

51 ... GaN layer 52 ... P type GaN layer

Claims (16)

An AlGaInN-based P-N diode device comprising a P-Al (x) Ga (y) In (y) N layer (x + y + z = 1) grown using NH3 as a Group V nitrogen precursor, The Group V nitrogen precursor further includes a hydrazine-based source that generates radicals capable of bonding with a hydrogen group during pyrolysis, and the P-Al (x) Ga (y) In (z) N layer has a hydrogen group separated from NH3. AlGaInN-based PN diode device characterized in that it is grown by being combined with the radical to be removed. Substrate, buffer layer grown on substrate, N-Al (a) Ga (b) In (c) N layer (a + b + c = 1), N-Al (a) Ga (b) In ( c) Active layer grown on N layer, P-Al (x) Ga (y) In (z) N layer (x + y + z = 1), N-Al (a) Ga (b) In grown on active layer (c) An AlGaInN-based PN diode device comprising an N-type electrode in electrical contact with an N layer and a P-type electrode in electrical contact with a P-Al (x) Ga (y) In (z) N layer, The P-Al (x) Ga (y) In (z) N layer is a nitrogen precursor that uses a hydrazine-based source that generates radicals capable of combining with ammonia and a hydrogen group during pyrolysis. An AlGaInN-based PN diode device obtained by being combined with a radical to be removed. A method of manufacturing an AlGaInN-based PN diode device comprising growing a P-Al (x) Ga (y) In (y) N layer (x + y + z = 1) using NH3 as a Group V nitrogen precursor. In The growth of the P-Al (x) Ga (y) In (z) N layer in this step is separated from NH3 by using NH3 as a nitrogen precursor and a hydrazine-based source that produces radicals that can bond with hydrogen groups upon pyrolysis. A method for producing an AlGaInN-based PN diode device, characterized in that the hydrogen group is combined with the radical to be removed. The method of manufacturing an AlGaInN-based P-N diode device according to claim 3, wherein the P-dopant used in the step comprises Mg. The method according to claim 3 or 4, The hydrazine-based source is a method of manufacturing an AlGaInN-based PN diode device, characterized in that to produce CH ₃ or NH ₂ radicals when pyrolysis. The method according to claim 3 or 4, Fabrication of AlGaInN-based PN diode device characterized in that the CH ₃ or NH ₂ radicals generated from the pyrolysis of the hydride source to combine with the hydrogen group (H) present in the reactor to reduce the concentration of the hydrogen group in the reactor Way. The method according to claim 3 or 4, A method of manufacturing an AlGaInN-based P-N diode device using a method of increasing the efficiency of nitrogen group supply by using a hydride source together with ammonia as the nitrogen precursor when forming a P-type AlGaInN layer. The method according to claim 3 or 4, The hydrazine-based source is a method of manufacturing an AlGaInN-based P-N diode device, characterized in that one selected from monomethyl hydrazine, dimethyl hydrazine, third butyl hydrazine. The method according to claim 3 or 4, The molar fraction (V (hydrazine) / III (Ga)) of the hydrazine-based source and gallium (Ga) in the step is 1 or more and 300 or less manufacturing method of the AlGaInN-based P-N diode device. The method according to claim 3 or 4, The molar fraction (V (ammonia) / III (Ga)) of the ammonia (NH ₃ ) and gallium (Ga) in the step is 100 to 8000 or less manufacturing method of AlGaInN-based PN diode device. The method according to claim 3 or 4, In the step, the growth temperature of the P-Al (x) Ga (y) In (z) N layer is 700 to 1100 ℃ the manufacturing method of AlGaInN-based P-N diode device. The method according to claim 3 or 4, The growth pressure of the P-Al (x) Ga (y) In (z) N layer in the above step is 20 to more than 760 torr, AlGaInN-based P-N diode device manufacturing method. The method according to claim 3 or 4, The method of manufacturing an AlGaInN-based P-N diode device, characterized in that for the carrier gas of the nitrogen precursor in the step using nitrogen or hydrogen or a gas mixed with nitrogen and hydrogen. The method according to claim 3 or 4, A method of manufacturing an AlGaInN-based P-N diode device, characterized in that the thickness of the P-Al (x) Ga (y) In (z) N layer grown in the step is 10 mW or more and 10,000 mW or less. The method according to claim 3 or 4, Two or more layers of P-Al (x) Ga (y) In (z) N layers having different (x, y, z) values are formed in a lamination, each having a thickness of 10 Angstroms or more and 10000. A method of manufacturing an AlGaInN-based PN diode device, wherein the AlGaInN-based PN diode element is formed to be less than or equal to 10 angstroms and not more than 10,000 angstroms. A method of manufacturing an AlGaInN-based PN diode device comprising growing a P-Al (x) Ga (y) In (y) N layer (x + y + z = 1) using NH3 as a Group V nitrogen precursor. In The growth of the P-Al (x) Ga (y) In (z) N layer in this step is separated from NH3 by using NH3 as a nitrogen precursor and a hydrazine-based source that produces radicals that can bond with hydrogen groups upon pyrolysis. By hydrogen group combined with the radical to be removed, The P-dopant used in the step comprises Mg, The hydrazine-based source is one selected from monomethyl hydrazine, dimethyl hydrazine, tertiary butyl hydrazine, In the step, the molar fraction (V (hydrazine) / III (Ga)) of the hydrazine-based source and gallium (Ga) is 1 or more and 300 or less, In the step, the molar fraction (V (ammonia) / III (Ga)) of the ammonia (NH 3) and gallium (Ga) is 100 or more and 8000 or less, In this step, the growth temperature of the P-Al (x) Ga (y) In (z) N layer is 700 ° C or more and 1100 ° C or less, In this step, the growth pressure of the P-Al (x) Ga (y) In (z) N layer is 20 tortor or more and 760 toror or less, In this step, nitrogen and hydrogen are used as a carrier gas of the nitrogen precursor, and the mixing ratio of hydrogen is 0% or more and 80% or less, In the P-Al (x) Ga (y) In (z) N (x + y + z = 1) layer, P-Al (x) Ga (y) In (z has different (x, y, z) values. A method of manufacturing an AlGaInN-based PN diode device, characterized in that consisting of N layers.