TW201530804A - Manufacturing method of gallium nitride crystallization and semiconductor element - Google Patents

Abstract

A manufacturing method of gallium nitride crystallization is provided in order to obtain Sphalerite type gallium nitride crystal having low lattice dislocation density, comprising steps: forming a Sphalerite type boron phophide crystal layer on the silicon substrate; forming an indium containing material layer on the Shphalerite type boron phosphide crystal layer to allow it to have a thickness of sufficiently retaining the Sphalerite type crystal structure; and forming the Sphalerite type gallium nitride crystal layer on the indium containing material layer. The indium containing material layer is an indium metal layer in which the thickness is within 4 atoms, an indium gallium nitride layer in which the thickness is within 2mm, an aluminum indium mixed layer in which the thickness is 4 atoms and aluminum atom containing is below 10%, or an aluminum indium gallium nitride layer in which the thickness is within 2mm and aluminum atom containing is below 10%. The lattice plane of the silicon substrate is preferably formed an inclined angle having above 3 degree and below 23 degree together with the lattice plane 100.

Description

Gallium nitride-based crystal and method of manufacturing the same

The present invention relates to a gallium nitride (GaN) crystal and a method of fabricating a semiconductor device, and more particularly to a method for forming a boron phosphide (BP) crystal on a cerium (Si) substrate and growing a zinc blende crystal thereon. A method of GaN-based crystals.

The gallium nitride-based crystal system is used in a short-wavelength light-emitting device. Generally, a gallium nitride-based crystal is epitaxially grown on a sapphire substrate. However, it is desirable to epitaxially grow a gallium nitride-based crystal having a low lattice difference density on a germanium substrate. Gallium nitride-based crystals can be classified into two types in terms of crystal structure. One is a wurtzite structure with excellent piezoelectric properties; the other is a sphalerite crystal which is suitable for data transmission or data processing with almost no piezoelectric properties. In general, the wurtzite structure is stable under high temperature growth. However, since metastable sphalerite crystals can promote good rebonding, in the case of use in a short-wavelength light-emitting device, the luminous efficiency of the device is remarkably improved, so the industry strongly expects a low lattice difference. A technique for growing sphalerite crystals at a discharge density. In addition, a gallium nitride-based crystal of a zinc blende structure having a low lattice difference density can be obtained, and a composite device of a short-wavelength light-emitting device and a semiconductor integrated circuit can be manufactured, and a future-type device having improved photoelectric characteristics can be developed. .

Prior to this, the inventors of the present application have published an example of directly forming a gallium nitride crystal on a boron phosphide crystal film formed on a germanium substrate. Li literature 1). However, by actually observing the gallium nitride crystals provided in Patent Document 1, it is found that irregularities, partial peeling, cracks, and the like appear on the surface thereof. An example of forming a gallium nitride-based crystal on a boron phosphide crystal film by using a boron phosphide crystal film formed on a germanium substrate as an intermediate layer is known in the prior art (Patent Document 2). However, the method disclosed in Patent Document 2 does not form a gallium nitride-based crystal having a zinc blende type crystal structure.

(previous technical literature)

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-235956

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-229601

The problem to be solved by the present invention is to provide a technique in which a zinc blende type boron phosphide crystal is used as an intermediate crystal on a lattice plane of ruthenium (100) to grow a low lattice difference density of zinc blende type nitrogen. Gallium-based crystals.

As an embodiment of the present invention, the present invention provides a method for producing a gallium nitride-based crystal, comprising: forming a zinc blende type phosphide boron crystal layer on a tantalum substrate; and a zinc blende type phosphorous boron crystal layer A layer containing an indium layer is formed to have a thickness capable of maintaining a zinc blende-type crystal structure; and a zinc blende-type gallium nitride-based crystal layer is formed on the indium-containing layer.

In an embodiment of the invention, the indium-containing material layer is preferably an indium metal layer having a thickness of 4 atomic layers or less.

In another embodiment of the present invention, the indium-containing material layer is preferably an indium gallium nitride (InGaN) layer having a thickness of 2 nm or less.

In still another embodiment of the present invention, the indium-containing material layer is preferably a mixed indium aluminide layer having a thickness of 4 atomic layers or less, and the aluminum atom (Al) content in the indium aluminide mixed layer is 10% or less.

In still another embodiment of the present invention, the indium-containing material layer is preferably an aluminum indium gallium nitride (AlInGaN) layer having a thickness of 2 nm or less, and the aluminum atom content in the aluminum indium gallium nitride layer is 10% or less.

In still another embodiment of the present invention, the indium-containing material layer is preferably formed by repeatedly depositing an Al _x In _y Ga _1-xy N layer and an Al _{x '} In _y' Ga _1-x'-y' N layer. Superlattice structure layer.

The lattice plane of the ruthenium substrate preferably forms an inclination angle of 3° or more and 23° or less with the (100) lattice plane.

According to an embodiment of the present invention, the present invention provides a method for producing a gallium nitride-based crystal, comprising: forming a sphalerite having a germanium atom concentration of 10 ¹⁷ cm ^-3 or more and 10 ²¹ cm ^-3 or less on a germanium substrate. a boron phosphide crystal layer; and a zinc blende type gallium nitride crystal layer formed above the zinc blende type boron phosphide crystal layer.

The present invention further provides a light-emitting device comprising a double heterojunction structure formed on a zinc blende type gallium nitride-based crystal produced by the above-described production method.

Furthermore, the present invention provides a method of fabricating a light-emitting device comprising an etching process for removing a germanium substrate from a zinc blende type gallium nitride-based crystal produced by the above-described manufacturing method. Among them, this etching process uses a zinc blende type phosphide crystal layer as an etch stop layer.

According to the present invention, a zinc blende gallium nitride crystal having a low lattice difference density can be grown on the (100) lattice plane of ruthenium with a boron phosphide crystal as an intermediate crystal.

10‧‧‧矽 substrate

11‧‧‧Phosphorus phosphide crystal film

12‧‧‧Indium metal film

13‧‧‧GaN film

14‧‧‧GaN film

121‧‧‧Indium gallium nitride film

122‧‧‧Indium Aluminide Mixed Film

123‧‧‧Aluminum indium gallium nitride film

124‧‧‧Superlattice structural layer

20‧‧‧n type connection layer

21‧‧‧n type cladding

22‧‧‧Active layer

23‧‧‧p-type cladding

24‧‧‧p type connection layer

30‧‧‧Substrate

31‧‧‧Aluminum film

Fig. 1 is a cross-sectional view showing the structure of a gallium nitride-based crystal grown in Examples 1 to 4 of the present invention.

Fig. 2 is a cross-sectional view showing a state of a gallium nitride-based crystal grown in Example 5 of the present invention.

3 is a graph showing the dependence of the lattice difference density of a gallium nitride-based crystal layer on the tilt angle of a germanium substrate according to an embodiment of the present invention.

4 is a cross-sectional view showing the structure of a semiconductor laser device produced by using a gallium nitride-based crystal obtained by a method for growing a gallium nitride-based crystal of Examples 1 to 5.

5 to 7 show a method for producing a high-brightness light-emitting diode using the gallium nitride-based crystal obtained by the method for growing a gallium nitride-based crystal of Examples 1 to 5.

Several embodiments for carrying out the invention are provided below to illustrate the objects and technical advantages of the invention. However, it is to be noted that the invention is not limited to the embodiments described below. The present invention can be implemented by various modifications of the embodiments described below without departing from the spirit of the invention.

[Example 1]

Hereinafter, a method of growing a gallium nitride-based crystal (Al _x In _y Ga _1-xy N crystal) disclosed in the first embodiment of the present invention will be described with reference to FIG. 1 .

First, an n-type germanium substrate 10 doped with a P-type dopant is prepared. The lattice plane of the germanium substrate 10 may be (100). However, in the present embodiment, a substrate having a slope of 6 degrees is sandwiched between the lattice plane and the lattice plane (110).

The temperature of the reaction furnace carrying the crucible substrate 10 was raised to 1000 ° C, and phosphine (PH ₃ ) and diborane (B ₂ H ₆ ) were introduced for about 1 hour to form a boron phosphide crystal film 11 having a thickness of about 500 nm. (intermediate crystallization). Since the temperature of the reactor is 1000 ° C, the germanium atom is diffused from the germanium substrate, and the germanium atom concentration of the boron phosphide crystal film 11 is about 10 ¹⁸ cm ^-3 . Thereafter, the substrate temperature is lowered.

The tantalum substrate 10 having the boron phosphide crystal film 11 formed on the surface thereof is not removed to the atmosphere, but is moved to another reaction furnace in a nitrogen atmosphere. The substrate temperature was raised to 1100 ° C and the surface was treated with hydrogen for 5 minutes. Next, the substrate temperature was lowered to 650 ° C, and trimethylindium ((CH ₃ ) ₃ In) was introduced, and the reaction time was only 1 second to deposit an indium metal film 12 having a thickness of about 1 atomic layer (about 0.5 nm).

After depositing the indium metal film 12, monomethyl hydrazine (CH ₃ -NH-NH ₂ ) and trimethylgallium ((CH ₃ ) ₃ Ga) are introduced into the reaction furnace for a reaction time of about 1500 seconds to deposit a thickness of about It is a 20 nm gallium nitride film 13.

After depositing a gallium nitride film 13 having a thickness of about 20 nm, the temperature of the reaction furnace is raised to 730 ° C, and monomethyl hydrazine and trimethyl gallium are introduced into the reaction furnace for a reaction time of about 3600 seconds to a deposition thickness of about 3,600 Å. A 1 μm gallium nitride film 14 is used.

The gallium nitride film deposited in the above manner has a crystal structure of a good zinc blende type having a lattice difference density of about 10 ⁶ cm ^-2 .

The reason why the zinc sulfide-type gallium nitride film can be formed by the film growth method described above is presumed to be as follows (but not intended to limit the present invention). Since the boron phosphide crystal film 11 formed on the tantalum substrate 10 is a zinc blende type, and the indium metal film 12 formed on the boron phosphide crystal film 11, the thickness is only about 1 atomic layer. Since the thickness of the indium metal film 12 is relatively small, the zinc blende type crystal structure can be maintained, so that the gallium nitride film formed thereon is also a zinc blende type. Actually, after depositing a gallium nitride film, an indium metal film 12 having a thickness of about 1 atomic layer is detected, which is an indium metal film having a dot-like appearance.

In the above method for growing a gallium nitride film, a gallium nitride film having a low lattice difference density can be formed for the following reason: a lattice constant of a boron phosphide crystal is about 0.454 nm, and a lattice of a gallium nitride crystal is used. The constant is about 0.451 nm. In the indium gallium nitride crystal, the higher the ratio of indium atoms, the larger the lattice constant. Indium gallium nitride crystals are substantially formed between the indium metal film 12 and the gallium nitride film formed by the above-described growth method, and can be resolved in the presence of indium gallium nitride crystal having a relatively large indium atom content. A problem of mismatch in lattice constant between boron phosphide and indium gallium nitride. Further, an indium gallium nitride crystal thin film having a relatively large indium content may be directly inserted between the boron phosphide crystal film 11 and the gallium nitride crystal film 13, and this embodiment will be described in detail in the second embodiment.

Although in the above-described method of growing a gallium nitride film, only an indium metal film having a thickness of about 1 atomic layer is formed, in other embodiments, an indium metal film having a maximum thickness of about 5 atomic layers is formed. Can get the same result.

[Example 2]

Hereinafter, a method of growing a gallium nitride-based crystal disclosed in Example 2 will be described with reference to Fig. 1 .

First, in the same manner as in the first embodiment, a boron phosphide crystal film 11 having a thickness of about 500 nm is formed on the p-type doped n-type germanium substrate 10.

The tantalum substrate 10 having the boron phosphide crystal film 11 formed on the surface thereof is not removed to the atmosphere, but is moved to another reaction furnace in a nitrogen atmosphere. The substrate temperature was raised to 1100 ° C and the surface was treated with hydrogen for 5 minutes. Next, the substrate temperature is lowered to 650 ° C, and monomethyl hydrazine, trimethyl gallium, and trimethyl indium are introduced, and the reaction time is 10 seconds to deposit a thickness of about 1 to several atomic layers (about 0.5 to 2 nm). Indium gallium nitride film 121. Since the thickness of the indium gallium nitride film 121 is thin enough, the crystal structure of the zinc blende type can be maintained.

After depositing the indium gallium nitride film 121, monomethyl hydrazine and trimethyl gallium are introduced into the reaction furnace at 1500 for about two seconds to deposit a gallium nitride film 13 having a thickness of about 20 nm.

After depositing the gallium nitride film 13 having a thickness of about 20 nm, the temperature of the reactor is raised to 730 ° C, and monomethyl hydrazine and trimethyl gallium are introduced into the reaction furnace for a reaction time of about 3600 seconds to deposit thickness. A gallium nitride film 14 of about 1 μm.

The crystal structure of the gallium nitride film deposited as described above is a good zinc blende structure having a lattice difference density of about 10 ⁶ cm ^-2 .

[Example 3]

Hereinafter, a method of growing a gallium nitride-based crystal disclosed in Example 3 will be described with reference to Fig. 1 .

First, in the same manner as in the first embodiment, a boron phosphide crystal film 11 having a thickness of about 500 nm is formed on the p-type doped n-type germanium substrate 10.

The tantalum substrate 10 having the boron phosphide crystal film 11 formed on the surface thereof is not removed to the atmosphere, but is moved to another reaction furnace in a nitrogen atmosphere. The substrate temperature was raised to 1100 ° C and the surface was treated with hydrogen for 5 minutes. Next, the substrate temperature is lowered to 650 ° C, and trimethyl indium and trimethyl aluminum ((CH ₃ ) ₃ Al) are introduced into the reaction furnace, and the reaction time is only 1 second, and the deposition thickness is about 1 atomic layer (0.5 nm). The indium aluminide mixed film 122 of the left and right). Since the indium aluminide mixed film 122 has a small thickness, the crystal structure of the zinc blende type can be maintained. In this embodiment, the gas flow rate can be adjusted so that the content of aluminum atoms in the gas is much smaller than the content of indium atoms in the gas.

After depositing the indium aluminide mixed film 122, monomethyl hydrazine and trimethyl gallium are introduced into the reaction furnace for a reaction time of about 1500 seconds to deposit a gallium nitride film 13 having a thickness of about 20 nm.

After depositing the gallium nitride film 13 having a thickness of about 20 nm, the temperature of the reaction furnace is raised to 730 ° C, and monomethyl hydrazine and trimethyl gallium are introduced into the reaction furnace for a reaction time of about 3600 seconds to a thickness of about 3,500 Å. It is a 1 μm gallium nitride film 14.

The crystal structure of the gallium nitride film deposited as described above is a good zinc blende structure having a lattice difference density of slightly more than about 10 ⁶ cm ^-2 . Moreover, compared with the conventional gallium nitride film, the surface roughness of the gallium nitride film deposited in this embodiment is relatively improved. The reason is presumed to be (but not intended to limit the present invention): when a gallium nitride film is grown, as long as a very small amount of aluminum atoms are present at the interface of the boron phosphide crystal film, the gallium nitride crystal is boron phosphide The adhesion rate of the crystal film is increased, and the gallium nitride crystal can be more reliably grown. According to the experimental results, the maximum content of aluminum atoms is preferably about 10% of the indium atom content. If the value exceeds this value, the lattice difference density will suddenly increase.

[Embodiment 4]

Hereinafter, a method of growing a gallium nitride-based crystal disclosed in Example 4 will be described with reference to FIG. 1 .

First, in the same manner as in the first embodiment, a boron phosphide crystal film 11 having a thickness of about 500 nm is formed on the p-type doped n-type germanium substrate 10.

The tantalum substrate 10 having the boron phosphide crystal film 11 formed on the surface thereof is not removed to the atmosphere, but is moved to another reaction furnace in a nitrogen atmosphere. The substrate temperature was raised to 1100 ° C and the surface was treated with hydrogen for 5 minutes. Next, the substrate temperature was lowered to 650 ° C, and monomethyl hydrazine, trimethyl gallium, trimethyl aluminum, and trimethyl indium were introduced, and the reaction time was 10 seconds to deposit a thickness of about 1 to several atomic layers ( An aluminum indium gallium nitride film 123 of about 0.5 to 2 nm. Since the thickness of the aluminum indium gallium nitride film 123 is small, the crystal structure of the zinc blende type can be maintained.

After depositing the aluminum indium gallium nitride film 123, monomethyl hydrazine and trimethyl gallium are introduced into the reaction furnace, and the reaction time is about 1500 seconds to deposit A gallium nitride film 13 having a thickness of about 20 nm.

After depositing the gallium nitride film 13 having a thickness of about 20 nm, the temperature of the reaction furnace is raised to 730 ° C, and monomethyl hydrazine and trimethyl gallium are introduced into the reaction furnace for a reaction time of about 3600 seconds for deposition. A gallium nitride film 14 having a thickness of about 1 μm.

The crystal structure of the gallium nitride film deposited as described above is a good zinc blende type having a lattice difference density of slightly more than about 10 ⁶ cm ^-2 . Moreover, compared with the conventional gallium nitride film, the surface roughness of the gallium nitride film deposited in this embodiment is relatively improved.

[Embodiment 5]

Hereinafter, a method of growing a gallium nitride-based crystal disclosed in Example 5 will be described with reference to FIG. 2 .

First, in the same manner as in the first embodiment, a boron phosphide crystal film 11 having a thickness of about 500 nm is formed on the p-type doped n-type germanium substrate 10.

The tantalum substrate 10 in a state in which the boron phosphide crystal film 11 is formed on the surface is not removed to the atmosphere, but is moved to another reaction furnace in a nitrogen atmosphere. The substrate temperature was raised to 1100 ° C and the surface was treated with hydrogen for 5 minutes. Next, the substrate temperature is lowered to 650 ° C, and the steps of: (1) introducing monomethyl hydrazine with trimethyl gallium and trimethyl indium, the reaction time is about 10 seconds to form a nitridation having a thickness of about 1.4 nm. Indium gallium layer; and step (2) introducing monomethyl hydrazine and trimethyl gallium for a reaction time of about 10 seconds to form a gallium nitride layer having a thickness of about 1.4 nm. Next, step (1) and step (2) are repeated four times in total. As a result, on the boron phosphide crystal film 11, a stack of five layers of indium gallium nitride/gallium nitride overlap stack (GaInN/GaN/GaInN/GaN/GaInN/GaN/GaInN/GaN/GaInN/GaN) is formed. The structure is such that a superlattice structure layer 124 having a total thickness of 14 nm and a crystal structure maintaining a zinc blende structure is formed.

After forming the superlattice structure layer 124, the temperature of the reaction furnace is raised to 730 ° C, and monomethyl hydrazine and trimethyl gallium are introduced into the reaction furnace for a reaction time of about 3600 seconds to deposit a thickness of about 1 μm. Gallium nitride film 14.

The crystal structure of the gallium nitride film deposited as described above is a good zinc blende structure having a lattice difference density of about 10 ⁶ cm ^-2 . By forming the superlattice structure layer 124 between the boron phosphide crystal film and the gallium nitride crystal, the lattice difference phenomenon occurring at the interface between the gallium nitride crystal and the boron phosphide crystal can be reduced, and The superlattice structure layer 124 has an effect of absorbing newly generated distortion, and thus it is possible to prevent the proliferation of new lattice difference rows.

In the above embodiment, the superlattice structure layer 124 is formed by laminating a film of indium gallium nitride and gallium nitride. However, the structure of the superlattice structure layer 124 is not limited thereto. In other embodiments of the present invention, the Al _x In _y Ga _1-xy N layer and the Al _{x '} In _y' Ga _1-x'-y' N layer may be repeatedly deposited to form different atoms. A superlattice structure layer in which a ratio of Al _x In _y Ga _1-xy N layers is stacked.

In the method of growing the gallium nitride-based crystals of the above-described first to fifth embodiments, only the phosphine and diborane are used to form the boron phosphide film; however, it is not limited thereto. In other embodiments of the present invention, phosphorus trichloride (PCl ₃ ) and boron trichloride (BCl ₃ ) may also be used to form a boron phosphide film. However, it is worth noting that when phosphine oxide and diborane are used to form a boron phosphide film, the quality of the gallium nitride-based crystal formed on the boron phosphide film is preferable. Further, in the above Examples 1 to 5, a monomethyl amide and a trimethyl gallium were used as raw materials to form a gallium nitride film, but in other embodiments of the present invention, trimethylgallium and dimethyl groups were used. The same good results were obtained with hydrazine as a raw material.

In the method of growing the gallium nitride-based crystals of the above-described first to fifth embodiments, the deposition of the gallium nitride crystal films 13 and 14 as an example of the gallium nitride-based crystal growth step is not limited thereto. In some embodiments of the present invention, the gallium nitride-based crystal may also be an Al _x In _y Ga _1-xy N crystal film of a different atomic ratio. The composition ratios of aluminum atoms and indium atoms are X and Y, respectively, and X and Y are values between 0 and 1, respectively.

(inclination angle of the substrate)

In the method for growing a gallium nitride-based crystal according to the first embodiment, the p-type doped n-type germanium substrate 10 has a lattice plane of 6 degrees with respect to the (100) lattice plane. Here, by changing the tilt angle of the lattice plane of the substrate and the (100) lattice plane, and measuring the lattice difference of the gallium nitride-based crystal layer grown on the boron phosphide crystal film through the indium-containing material layer Density, the result shown in Figure 3 can be obtained. In FIG. 3, the vertical axis represents the lattice difference density of the gallium nitride-based crystal, and the horizontal axis represents the inclination angle of the lattice plane of the germanium substrate and the (100) lattice plane. It can be understood from Fig. 3 that when a ruthenium substrate having a tilt angle of 0° is used, the lattice difference density is 10 ¹⁰ cm ^-2 ; however, when the tilt angle exceeds 3°, the lattice difference density is rapidly reduced to 10 ⁶ cm. ^-2, while the tilt angle exceeds 23 °, the lattice dislocation density increases again. Further, when the inclination angle exceeds 23°, irregularities are generated on the growth surface. Therefore, the inclination angle of the ruthenium substrate is preferably 3° or more and 23° or less. Further, from the viewpoint of the lattice difference density, the most suitable tilt angle is 6° or more and 10° or less.

(composition tilt)

In the method of growing the gallium nitride-based crystal of the second embodiment described above, only the gallium nitride layer 13 is formed on the indium gallium nitride layer 121. However, in other embodiments, the proportion of indium atoms in the indium-containing material layer may be adjusted during the growth of the indium-containing material layer. For example, at the start of growth, the indium atom content ratio X in the indium _- containing material layer (In _x Ga _1-x N) is increased by 0.15 or more, and the content of indium atoms is reduced as the growth time progresses. However, it is worth noting that the growth step described above must be carried out at a growth temperature of 700 ° C or lower, for example, about 650 ° C. If the growth temperature is high, a sufficient amount of indium atoms cannot be introduced.

(矽 atomic concentration of boron phosphide crystal film)

In the method of growing the gallium nitride-based crystals of the above-described first to fifth embodiments, it is preferable that the boron phosphide crystal film 11 contains a relatively high concentration of germanium atoms. Since the bonding between the germanium atom and the boron atom is very strong, it is possible to suppress the lattice difference expansion and proliferation generated in the boron phosphide crystal film 11. It is worth noting that the concentration of germanium atoms is preferably 10 ¹⁷ cm ^-3 or more and 10 ²¹ cm ^-3 or less. If the germanium atom concentration is 10 ¹⁷ cm ^-3 or less, the lattice difference density of the grown gallium nitride crystal increases. If the germanium atom concentration is 10 ²¹ cm ^-3 or more, unevenness may occur on the surface of the grown gallium nitride crystal.

In still other embodiments of the present invention, an extremely thin high concentration cerium doped layer may be provided in the phosphide crystal film 11. Specifically, a boron phosphide crystal film having a thickness of about 100 nm is formed on the tantalum substrate 10, and a thickness of about 1 to 3 nm (a few atomic layers) is formed thereon, and a germanium atom doping concentration is about 10 ²¹ cm ^{- 3} silicon doped with a high concentration of boron phosphide crystal layer, and then a thickness of about 400nm of the boron phosphide crystalline film thereon. Since the high concentration lanthanum-doped phosphide crystal layer is sandwiched by the upper and lower two boron phosphide crystal films, the interface between the ruthenium substrate 10 and the phosphide film 11 or the phosphide film (bottom) can be suppressed. The lattice difference expansion and proliferation can further reduce the lattice difference density of the gallium nitride-based crystal above the indium-containing material layer. Compared with the gallium nitride-based crystal formed by the prior art, the lattice difference density is greatly reduced.

(low temperature annealing)

In the method of growing the gallium nitride-based crystals of the above-described first to fifth embodiments, the tantalum substrate 10 having the boron phosphide crystal film 11 formed on the surface thereof is not removed to the atmosphere, but is moved to a state in a nitrogen atmosphere. Other reaction furnaces, after which The substrate temperature was raised to 1100 ° C and the surface was treated with hydrogen for 5 minutes.

Preferably, after this, the first low temperature annealing is performed by lowering the temperature of the reactor to below 700 ° C, for example, 650 ° C, and for about 10 minutes. Further, it is preferable to form each layer of the indium-containing material layer, for example, after forming the indium metal film 12, the indium gallium nitride film 121, the aluminum indium gallium nitride film 123, and the superlattice structure layer 124, or forming nitridation. After the gallium film 13, the temperature of the reaction is maintained at a temperature below 800 ° C, for example, 750 ° C for several tens of minutes, whereby a second low temperature annealing is performed. By performing the first and second low temperature annealing as described above, the crystallinity of the boron phosphide crystal film 11 or the gallium nitride film 13 can be improved, and the defect density of the surface can be lowered. As a result, the lattice difference density of the gallium nitride film 14 can be further reduced.

[Embodiment 6]

4 is a cross-sectional view showing the structure of a semiconductor laser device produced by using a gallium nitride-based crystal obtained by the method for growing a gallium nitride-based crystal according to the first to fifth embodiments.

As previously mentioned, the gallium nitride film 14 is an undoped layer. First, an n-type connection layer 20 made of gallium nitride doped with germanium atoms and having a thickness of about 1 μm is formed thereon. Next, on the n-type connection layer 20, an n-type cladding layer 21 made of aluminum gallium nitride and doped with germanium atoms and having a thickness of about 0.1 μm is formed. On the n-type cladding layer 21, an active layer 22 is formed. In the present embodiment, the active layer 22 is formed by a gallium nitride layer having a thickness of about 2 nm/an indium gallium nitride layer having a thickness of about 2 nm and laminated in a 6-cycle manner, and a superlattice having a total thickness of about 24 nm. Structural layer. The active layer 22 is also an undoped layer. Next, on the active layer 22, a p-type cladding layer 23 made of aluminum gallium nitride and doped with magnesium (Mg) is formed, and a gallium-doped gallium nitride is formed thereon, and the thickness is formed. The p-type connection layer 24 is about 400 nm. Then, by etching process, a part of the n-type connection layer is removed. 20, the n-type cladding layer 21, the active layer 22, the p-type cladding layer 23 and the p-type connection layer 24, with a strip-shaped region having a width of about 5 μm as a laser oscillation region, followed by the remaining n-type An electrode is formed on the connection layer 20 and the p-type connection layer 24.

Since the semiconductor laser element thus obtained uses zinc oxide crystal of zinc blende type, the efficiency of re-bonding of holes and electrons is good, and thus a semiconductor laser element having high luminous efficiency can be obtained. Further, in the case of forming an optical element such as a semiconductor laser element using a zinc iodide-type gallium nitride crystal layer, since the mobility of the hole is extremely high, the n-type cladding layer can be said to prevent the occurrence of hole leakage. It is a necessary structure. Therefore, the semiconductor laser element provided in this embodiment preferably has a double heterojunction structure.

[Embodiment 7]

5 to 7 show a method of producing a high-brightness light-emitting diode (LED) using the gallium nitride-based crystal obtained by the method for growing a gallium nitride-based crystal of Examples 1 to 5.

As described above, the gallium nitride film 14 is an undoped layer. First, an n-type connection layer 20 made of gallium nitride doped with germanium atoms and having a thickness of about 1 μm is formed on the gallium nitride film 14. Next, on the n-type connection layer 20, an n-type cladding layer 21 made of aluminum gallium nitride and doped with germanium atoms and having a thickness of about 0.1 μm is formed. On the n-type cladding layer 21, an active layer 22 is formed. In the present embodiment, the active layer 22 is formed of a gallium nitride layer having a thickness of about 2 nm/an aluminum gallium nitride layer having a thickness of about 2 nm and laminated in 6 cycles, and a superlattice having a total thickness of about 24 nm. Structural layer. The active layer 22 is also an undoped layer. Next, on the active layer 22, a p-type cladding layer 23 made of gallium nitride and doped with magnesium atoms is formed, and a gallium nitride doped with magnesium atoms is formed thereon, and the thickness is about The p-type connection layer 20 of about 400 nm (the structure formed so far has the same appearance as the semiconductor laser element of the sixth embodiment).

In order to make the light-emitting diode having the double heterojunction structure high in brightness, it is preferable to remove the germanium substrate 10 so as not to absorb the generated ultraviolet light to blue light. Here, the phosphide crystal layer 11 is used as an etch stop layer for etching, and the ruthenium substrate 10 is removed. In the present embodiment, potassium hydroxide (KOH) at 500 ° C can be used as an etching solution, thereby achieving a better selection ratio between the ruthenium substrate 10 and the phosphide crystal layer 11 (as shown in FIG. 5 ). ). Further, in another embodiment, a dilute liquid or a hydrazine solution of a mixed solution of hydrogen fluoride and nitric acid was used as an etching liquid to etch the ruthenium substrate, and similarly good results were obtained.

Next, the boron phosphide crystal layer 11 is removed. Here, it is necessary to select an etching solution which can achieve a preferred ratio between the boron phosphide crystal layer and the gallium nitride layer (the layer containing the very thin layer containing In). In the present embodiment, a mixed solution of potassium hydroxide, sodium hydroxide (NaOH), and magnesium oxide (MgO) heated to 500 ° C was used as an etching solution to remove the boron phosphide crystal layer.

Further, although in other embodiments, phosphoric acid heated to 500 ° C may be used to remove the boron phosphide crystal layer; however, from the relationship between the etching rate and the selectivity, it is preferred to use potassium hydroxide or sodium hydroxide. And a mixed solution of magnesium oxide is used as an etching solution to remove the boron phosphide crystal layer.

Next, the undoped gallium nitride film 14 is removed by etching. In the present embodiment, the gallium nitride film 14 can be removed using potassium hydroxide at 500 ° C as an etching solution, thereby exposing the n-type connection layer 20 having a high conductivity. Figure 6 shows this status.

Next, an adhesive member including an substrate 30 and an aluminum film 31 formed on the surface of the substrate 30 by sputtering is prepared. Among them, the aluminum film 31 has a property of reflecting ultraviolet rays to blue light. Next, the n-type connection layer 20 is bonded to the bonding member. Among them, an alloy of aluminum and indium is used, and it is pressed at 400 ° C to complete it. Engage. Figure 7 shows this status.

The substrate in which the high-intensity light-emitting diode formed by the above method is integrated is separated into a plurality of individual light-emitting diodes by a die cutter. Subsequently, and carried on a package (not shown), a phosphor that converts ultraviolet or blue light into white light surrounds the light-emitting surface of the light-emitting diode (as shown in the top surface of FIG. 7), thereby Finish the product.

As described above, the present invention can obtain a zinc blende type gallium nitride-based crystal having a low lattice difference density, and can form a high-efficiency light-emitting device made of the zinc blende type gallium nitride-based crystal.

10‧‧‧矽 substrate

11‧‧‧Phosphorus phosphide crystal film

12‧‧‧Indium metal film

13‧‧‧GaN film

14‧‧‧GaN film

121‧‧‧Indium gallium nitride film

122‧‧‧Indium Aluminide Mixed Film

123‧‧‧Aluminum indium gallium nitride film

Claims (11)

A method for producing a gallium nitride-based crystal, comprising: forming a zinc blende type phosphide crystal layer on a germanium substrate; forming an indium-containing layer on the zinc blende type boron phosphide crystal layer And having a thickness capable of maintaining a zinc blende type crystal structure; and forming a zinc blende type gallium nitride crystal layer on the indium containing layer. The method for producing a gallium nitride-based crystal according to the first aspect of the invention, wherein the indium-containing material layer is a metal indium layer having a thickness within 4 atomic layers. The method for producing a gallium nitride-based crystal according to the first aspect of the invention, wherein the indium-containing layer has an indium gallium nitride layer having a thickness of 2 nm or less. The method for producing a gallium nitride-based crystal according to claim 1, wherein the indium-containing layer is an indium aluminide mixed layer having a thickness within 4 atomic layers, and the indium aluminide mixed layer The aluminum atom content is 10% or less. The method for producing a gallium nitride-based crystal according to claim 1, wherein the indium-containing layer is an aluminum indium gallium nitride layer having a thickness of 2 nm or less, and the aluminum indium gallium nitride layer is The aluminum atom content is 10% or less. The method for producing a gallium nitride-based crystal according to the first aspect of the invention, wherein the indium-containing layer is repeatedly deposited with an Al _x In _y Ga _1-xy N layer and an Al _{x '} In _y' Ga _1-x A superlattice structure layer composed of _'-y' N layers. The method for producing a gallium nitride-based crystal according to the first aspect of the invention, wherein the ruthenium substrate has a lattice plane and forms an inclination angle of 3° or more and 23° or less with the (100) lattice plane. The method for producing a gallium nitride-based crystal according to the first aspect of the invention, wherein the zinc oxide crystal layer of the zinc blende type has a germanium atom concentration of 10 ¹⁷ cm ^-3 or more and 10 ²¹ cm ^{-3 .} the following. A method for producing a gallium nitride-based crystal, comprising: forming a zinc blende type phosphide crystal layer having a germanium atom concentration of 10 ¹⁷ cm ^-3 or more and 10 ²¹ cm ^-3 or less on a substrate; A zinc blende-type gallium nitride-based crystal layer is formed over the zinc blende type boron phosphide crystal layer. A light-emitting device comprising the above-described zinc blende type gallium nitride-based crystal produced by the method for producing a gallium nitride-based crystal according to claim 1 or 9 A pair of heterojunction structures. A method of manufacturing a light-emitting device, comprising: an etch process for producing the zinc sulphide type gallium nitride manufactured by the method for producing a gallium nitride-based crystal according to claim 1 or 9 The ruthenium substrate is removed by crystallization, wherein the strontium phosphate type phosphide crystal layer is used as an etch stop layer.