TW398083B - The nitride semiconductor light emitting element and its manufacturing method - Google Patents

Abstract

This is a nitride semiconductor light emitting element, which uses the indium-containing group III nitride semiconductor layer as a layer. Such semiconductor layer is composed of the multiple phase structure, which is consisted of one major phase and a multiple sub-phases. The major phase and the sub-phases have different quantity of indium. The subsystem is composed of indium crystals; a strained layer surrounds the interface of the crystal and the main phase.

Description

-1¾. 87121: _correction 5 Description of the invention Different. The first example 7nm is f 丨 Chu T ~ Z ~ 'H, the example 18_ is the maximum. The ratio is the smallest, and the example is 9 nm, which is comparatively implemented. Although the present invention has been described, the fLED ’s emitted light lacks monochromaticity. It is not used to limit the preferred embodiment to reveal such as the scope of the spiritual toilet, and anyone who knows this technology can make some modifications and modifications without departing from the second example of the present invention. The scope of this month shall be subject to the scope of patent application attached. Description of this wool symbol: 2, 10 ~ 2 light-emitting layer; u ~ stacked layer; 21, 2 (n ~ main phase; 22, bit; 23 ~ stretch layer; 50 ~ LED; 100 ~ substrate; 100 & low temperature, -f_a, 10 1 ~ N-type gallium nitride layer; 1 03 ~ mixed crystal layer; 103 g ~ gallium nitride layer, 104 ~ gold foil electrode; i 04a ~ nickel oxide thin film electrode; 105 ~ p type electrode; 109 ~ N type electrode; 203 ~ stretched layer.

V. Description of the Invention (1) The present invention relates to a nitride semiconductor light-emitting element, which uses an indium-containing nitride semiconductor layer as a light-emitting layer. The semiconductor layer is composed of a main phase and a plurality of sub-phases. Multiphase structure and the main phase and the subphases have different indium contents. The invention also relates to a method for manufacturing the element. _ The gaseous semiconductor light-emitting element uses an indium-containing group III nitride semiconductor expressed as AlxGayInzNal ^ _a (x + y + z = 1, OSx, y < 1, 0 < zSl, 0 &a; 1). As a light-emitting layer, a high-frequency light is emitted. In particular, a mixed crystal of gallium indium nitride (GabInibN: the main component material of the OASD-based light-emitting layer (see Japanese Patent Publication No. 55-3834). An example of the conventional technology of the present invention is the use of an indium content of 2%. % Of gallium steel nitride mixed crystal as a light emitting layer and a blue light emitting diode emitting light with a wavelength of 45 nm and a gallium indium nitride mixed crystal containing 45% of indium as a light emitting layer A green light-emitting diode with a wavelength of 525 nm.

The osmium indium nitride mixed crystal can also be used as a light emitting layer for a single or multiple well region structured well region layer (see Japanese Patent Publication No. 9-3 6430). The gallium-indium-nitride mixed crystal used as the light-emitting layer until now is generally considered to have a uniform indium content (see Japanese Patent Gazette Nos. 9 to 36 4 30). However, recently, it has been found that a gallium indium nitride layer with an uneven indium content is advantageous for use as a light emitting layer (see Japanese Patent Gazette No. 1 0-1 0731 5). This so-called heterogeneous structure of gallium indium nitride is composed of phases with different indium contents. Such a high-density light-emitting system of a gallium-indium-nitride layer having the above-mentioned multi-phase structure is a kind of light emitting unit such as a quantum dot (qUantum dots). _

Sixth, the scope of patent application 1. A nitride semi-conductor semiconductor layer as a multi-phase multi-phase indium content indium content 'special component of the device' the crystal and the main phase 2. If a patent is applied The feature is that the width of the sub-phases is 0.5x D or shorter. 3. If the feature of the patent application is within the range of the stretched layer.

Number 87121RM

Conductive light-emitting element, ϊ1 indium-containing m-group nitrided light layer, the semiconductor layer is composed of a main phase and a complex structure, and the main phase and the sub-phases have different characteristics because the sub-phases are mainly composed of crystals. The boundary of the structure is surrounded by a stretched layer. The element described in item 1, wherein the element is mainly composed of a crystal, and the crystal has a stretched layer 'D which represents the full width of the subphase. The element described in item 1, wherein the thickness of one of the elements is one of between 5 angstroms and 10 nm. 4 · The element described in claim 1, 2 or 3 of the patent scope, wherein It is characterized in that the number of the sub-phases having the stretched layer accounts for more than 50% of the total number of the phases. _ 5. The element according to item 1, 2 or 3 of the scope of patent application, wherein the element is characterized in that one of the sub-phases has a density of 2〆10 cm 3 or less. 6. The element according to item 1, 2, or 3 of the scope of patent application, wherein the element is characterized in that one of the light emitting layers has a thickness between ΐηη and 300nm.

7. A nitride semiconductor light-emitting device ^ manufacturing method 'The device uses a steel-containing group III nitride semiconductor layer as a light-emitting layer, wherein the semiconductor layer is a multi-phase structure composed of a main phase and a plurality of sub-phases And the main phase and the nettle phase have different indium contents, the method is characterized by the following steps: z The light-emitting layer is heat-treated at a heat treatment temperature, and the heat treatment

2000. 04.18. 022 V. Description of the invention (2) The structure of the gallium indium nitride layer is usually composed of A ^, and the main phase accounts for this, the target (moment / phase), and the subphase phase bulletin No. 10-56202. . Subphase damage / product (refer to the Japanese incorporation of indium content. In the subphase t, there is a difference between the main phase and the main phase, and the subphase is scattered in the main phase = the amount is also different. (Subphase ) And the main phases around it; formed in microcrystal No. 1 .-_ 5). Microcrystalline]: Two: of: ί is enough to be-a quantum dot. : Generally believed that = the light emitting layer composed of a sub-group nitride semiconductor enters = in: the light emission of the light-emitting layer composed of an indium-containing melon nitride semiconductor is emitted: :: some sub-phases (quantum dots), but the lack of The '= stable first emission characteristic (meaning stable emission density and wavelength): The main reason for quantum is that it is impossible to know clearly the sub-phase as the demand condition. Therefore, in order to obtain stable emission, it is necessary to clearly understand the requirements for effectively using the sub-phase as the sub-point in high-density light emission. The present invention is to provide a compound semiconductor light-emitting device by clarifying the conditions from the viewpoint of the above-mentioned problems, and it can provide stable and excellent emission characteristics' as well as a manufacturing method thereof. The present invention defines a region between each sub-phase and its main phase, so that the microcrystals constituting the sub-phase can be used as a quantized light-emitting unit. 5. Description of the invention (3). Special I, the present invention is a nitride semiconductor light-emitting element using a steel-containing Group VIII nitride semiconductor layer as a light-emitting layer, the j-by-main phase and a plurality of sub-phases, and a multi-phase structure and the The sub-phases such as the main layer J have different contents of indium, and the fhai element is characterized by these sub-phases: = composed of crystals, and the boundary between the crystals and the main phases is stretched: the invention also provides A method for manufacturing a nitride semiconductor light-emitting device is disclosed. A light emitting device using an indium-containing melon nitride semiconductor layer as a light emitting device is provided.

Ll 嫱 I: The semiconductor layer is composed of a main phase and a plurality of sub-phases :: junction, and the main phase and the sub-phases have the same indium content, the following steps of the method: The light-emitting layer is subjected to J treatment at a heat treatment temperature: the heat treatment temperature is between 950 and 120 (rc; the light is emitted. It is cooled from the heat treatment temperature to 950 c at a speed of 20 C or more of the master knife clock. The light-emitting layer is cooled from 95 ° at a speed of less than 20t per minute to a to form a plurality of stretched layers at a plurality of boundaries between the main phase and the sub-phases. In the present invention, since each sub-layer The phase is mainly composed of a crystal with a stretched layer between the two phases, so the stretched layer increases the emission density. Therefore, the sub-phase C:: 层 之 = 彳 卜 ί 地As a quantized emission medium, the high-frequency visible light emitted by the semiconductor light-emitting element has high emission intensity and excellent monochromaticity. Brief Description of the Drawings Figure 1 represents a method of using the electron microscope to the invention. Nitride semiconductor

Page 6 V. Description of the invention (4) _ Photographing of the light-emitting layer of a bulk light-emitting element ^ Figure 2 is an example of a lattice image obtained by the first-present invention. Schematic of the structure. The stacked layers of the light-emitting element of the example only. FIG. 3 represents a gas-photograph taken of the nitride of the first embodiment using a light-emitting layer of an electric semiconductor light-emitting element to enter the mirror. Lattice image. Fig. 5 shows the first embodiment; = two two embodiment plan view of the elements. In the following description, ‘phase’ refers to a species that occupies in space < 1 ί = approximately: the phase of a crystal containing a fine amount (concentration). IS:: II; II: m ′, and in contrast, the phase occupying a small space area is a child. The sub-phases can be almost evenly distributed in 2 or unevenly in the area near the connection zone with other layers. The sub-phases are not distinguished by their indium content, but by the main magnitude. The main phase system of Jingbogong is mainly composed of a single crystal of "Luxing structure" obtained by stacking many single crystal layers. In some cases, the main phase partially contains a silicon region or an amorphous silicon region. Regardless of the form of the crystal, the main phase is

Occupies a large area. Almost all sub-phases are small crystals (micro-body). The microcrystalline system is composed of single crystals or polycrystals, or the county is not equal to the human body. The microcrystal may be a mixture of these substances. The shape of n, α and 儆 crystals is usually approximately spherical or polygonal. The diameter of the sub-phase is about several tens of tens of nm 'or, in the case of an island, its width is between several tens of nm and ten runs. Although the number is quite large " m to dozens of ^^ of the two sedimentation 7

Page 7 V. Description of the invention (5) Indium nuclei deposited on the connection bands of other layers occur, but in the present invention-a crystal system of about several nm to several tens of nm is considered as a subphase. In the present invention, the light emitting layer is formed of an indium-containing group III nitride semiconductor having a multiphase structure composed of a main phase and a subphase. The thickness of the material forming the main phase is the thickness of the light-emitting layer. When the light-emitting layer has an excessively thinner thickness than that of the layer, it loses layer continuity. The light-emitting layer H formed by the discontinuous layer will reduce the forward bias of the light-emitting element and cause adverse shadowing. 'Therefore, the thickness of the light-emitting layer must be between 1 and 300 nπ1. Zhi Yue.

U. The light-emitting layer may be formed of an indium-containing m-group azeotrope conductor doped with impurities intentionally. The light emitting layer may also be formed of a human m-type nitride semiconductor which is not intentionally doped with impurities. In addition, the # 光 层 can also be formed by stacking layers of doped :: heterolayers. From the standpoint of emission density, the light-doped layer must be made thicker. Its thickness must be between about ο and 300 nm / the undoped layer must be thin, and its thickness is between about 1 and 10 nm. Say

The conductive form of the light emitting layer must be n-type. This is because the transfer of carriers (especially theft electrons) between the main and sub-phases determines the emission density. So it is best to use electricity for the I optical layer? As the main carrier, the light emitting layer is of the n-type. The carrier concentration of the light-emitting layer is preferably set to less than 1 × ΐ ~,: J = at 1 × 1019c: 3. The carrier concentration of the main phase and the sub-phase is not constant-it is necessary that the carrier concentration of the sub-phase 'main phase may be about 1 X 1018 cm-3 and = about 1 X 1 ° 17 Cm-3. Regardless of the main phase and the sub-phase can be-in: 3 is different, in the entire light-emitting layer, the carrier concentration "e" is again in the above range. The sub-phase is generated from within the main phase. For example, the sub-phase is from

V. Description of the invention (6) The tensile region scattered in the main phase, which is derived from the marriage nucleus in the main phase, is a region of crystal defects. When the density of the main phase neutron phase becomes large, the light emitted from the main phase lacks monochromaticity. When the density of the sub-phase exceeds 2 X 1 018cnr3, the monochromaticity of the emitted light will decrease rapidly. Therefore, the density of the sub-phases must be set below the above-mentioned density. In particular, in an undoped light-emitting layer having a thickness of 20 n in or less, the density of the sub-phases is preferably set to 5 x 1023 Xt (t: thickness) or less. If the density of the sub-phases is set within the above range ', it is possible to obtain emitted light having a width of 15 nm—half or less \ with excellent monochromaticity.

In some cases, a light-emitting layer formed from an indium-containing m-group nitride semiconductor grown by MOCVD between 950 ° C and 6 50 ° C can be divided into many phases in an as-grown state . However, the sub-phases are very inconsistent in many phases with growth-like odors. When the growth-like semiconductor nitride-containing semiconductor layer is heat-treated, the sub-phases are stably generated, and the main phase is used as a source phase, and a multi-phase structure is thus generated. In a hafnium-containing heat treatment method capable of stably forming a multi-phase and used as a light emitting layer, the temperature rise rate of the heat treatment temperature from the growth temperature of the light emitting layer to the heat treatment temperature of the hafnium can be maintained. J =

-Cause of warfare. I-rate cooling rate is the best & the sub-phase size is doubled. The magnitude of the thousand phase and the indium-containing property and the monochromaticity of the emitted light increase. In the present invention, the structure of the M-wavelength-the structure in the present invention is particularly pulled by the sub-phase-the connection between the main phase and the sub-phase of the earth layer. In particular, the characteristic area of the child phase of the present invention is maintained between the child phase and the surrounding main phase. V. Description of the invention (7) Parent junction. Moreover, the sub-phases having such a stretched layer account for more than 50% of all sub-phases. ^ In the heat treatment of the light emitting layer, the sub-phases having the surrounding stretched layer can be formed by appropriately adjusting the rate of cooling down from the heat treatment temperature. A better cooling method is to change the temperature from 950,000 t to 1200 when changing the temperature drop rate. The temperature of the heat treatment between the two is reduced. The preferred heat treatment temperature range is from 95 ° to 1 = 0 0. (: Between. In particular, the cooling method includes cooling the light-emitting layer from the heat treatment temperature to 95 ° C at a rate of 20 c or more per minute and the light-emitting layer from 95 ° C at a rate of 20 ° C per minute or less. It is cooled to 65 °, thereby stably forming the sub-phases with a stretched layer around. By this method, the proportion of the sub-phases with a stretched ^ can easily reach 50% or more. It can be photographed by a computational electron microscope The lattice phase has the sub-phase 1 of the stretched layer to obtain the proportion of the sub-phase. When the temperature is reduced from the heat treatment temperature to 950 ° C at a rate of 20 ° C or less per minute, the surface shape of the light-emitting layer, The method keeps well and causes the light-emitting layer to be uneven. When the temperature is lowered from 95 ° C to 65 ° C, rapid cooling at a speed exceeding 20 per minute is disadvantageous because it causes too much stretched layer around the sub-phases. The multi-phase heat treatment does not have to be performed separately. The formation of a multi-phase structure can also be performed simultaneously when an aluminum gallium nitride layer is formed on a light-emitting layer composed of an indium-osmium group nitride semiconductor layer. This is because Therefore, the growth temperature of the growth layer on the light-emitting layer is within the above-mentioned preferred heat treatment temperature range. The general cross-section electron microscopy technique can be used to confirm whether the indium-osmium-containing nitride semiconductor has a multi-phase structure. Gallium indium formed with multi-phase structure V. Description of the invention (8) The mixed crystal part of the rat compound is photographed as the crystal defect is also black. It is usually judged whether it is a dense neutron phase with a component analyzer and The difference in the content of the sub-phases can also be seen in the micro-images of the sub-phases. See the effect. The bright black will cause a linear sub-phase. The amount of steel can be analyzed to accurately stretch the cross-section of the magnification region. Electron microscopy images of spheres or polygons. In a black image, such as a tomography. We can also know the shape of the subphase by the black image. The electron microscope can be determined by the density of the black image, such as EPMA. The main phase The X-ray diffraction method of the sub-element is known that the t-stretch layer can obtain the 'sub-phase' in some cases from the high magnification transverse ratio in millions of times. The shape of the image formed by the layer comes. The main phase is broken. Use one. The electrons in each section of the main phase show the best view of the indium-containing section. Figure 1 represents an electron microscope for the nitride semiconductor light-emitting device of the present invention. An example of a lattice image obtained by shooting the light-emitting layer. Its magnification is 2 X 106. The following description will be given in conjunction with this figure. The light-emitting layer 2 has a multi-phase junction consisting of a main phase 21 and a sub-phase 22, This sub-phase has a different indium content from the main phase. In the main phase 21, there is a stretching layer 23 around the mother-sub-phase 22 as a matrix. In particular, the sub-phase 22 is located between it and the main phase 21 The junction has a crystal of the stretched layer 23. Although the thickness 廿 L of the stretched layer 23 around the sub-phase "is usually the same, it is not absolute. For example, in some cases, the stretch layer 23 is twisted so that one side is thicker. When the lattice gaps are compared, it is found that the lattice gaps in the main phase 21, the phase 22, and the tensile layer 23 are different. In particular, pull

Page 11 5'Invention description (9) The lattice plane of the stretched layer 2 3 is called Shidan, 2 2 ^ ί; (02 3 Λ " Ρ ": ^ ^ ^ ^ ^ ^ ^ ^ ^ Κ 申The lattice image of layer 23 is between meta-position 22, and its lattice is sometimes distorted. The optical density of the second phase in the main phase 21 and the sub-phase stretching layer 23 in the sub-phase 3 @ + layer has an effect. When the pull comes from Multi-phase structure luminous emission density enhancement effect. This kind of thick 1 "3 2 2 is available in XD or less, where D is a sub-phase 2 and if the sub-phase 22 is an island, D is the width. For example or smaller. L, The thickness of the tensile layer 23 with a spherical phase of nm is 10 nm and 2 == 23, the thickness is not always the same, but even if the loss is: But Η: know fdegree 疋 0.5 XD or more The effect will not be reduced if the hour is too small: 'I-4 layer 23 will not have a high emission density enhancement effect when it is very thin: 23 if! Some stretch layers 23 are not in the main phase 21 and the sub-phase I ,! u, a band structure that generates quantized carriers that can cause high-density light emission; .... the thickness of the tensile layer 23 must be at least 5 angstroms, and preferably 10 angstroms or more. The maximum thickness d should be 10 nm or less This is determined based on the indium content of the hafnium-containing nitride semiconductor semiconductor, which is usually used as a light-emitting layer, of about 5% to 10%. Therefore, the thickness d of the stretched layer 23 should be between 5 Angstroms and 10 nm. As described above, after the indium-containing nitride semiconductor layer used as the light-emitting layer is grown into a bundle, the thickness d of the stretched layer 23 can be adjusted by heat treatment of the light-emitting layer 2 to produce a multi-phase structure. The temperature drop rate in the cooling step comes from the fifth, description of the invention GO) control. The temperature drop rate from 950 t to 650 ° C is the main factor of the temperature. The temperature drop rate in this range should be In the heart :: 23 thick. By setting the temperature drop rate at 5 tr per minute C or more preferably between rc, 15, you can form -c of :: the better between The stretch layer 23. At the same time, in this cooling ^, ^ the percentage of the sub-phase of the stretch layer can easily exceed 'drop, when there is more than 20 t per minute, the thickness of the stretch layer will increase and report difficulties; The drop rate is below 0.5 XD. Conversely, when the temperature drop rate is less than 5 per minute, the degree d will decrease ', and if it is less than 3t per minute, the stretching The thickness will be less than 5 angstroms. In the temperature drop rate of the above cooling step, another type can be used: for example, from 95 ° to 65 °, a fixed speed can be performed. : To 80 = come Γ: so that the temperature is reduced to 800 c at a rate of 15 ° c per minute, and from 80.0 to 10 minutes at a rate of 10 minutes of the mother minute. Good results are obtained. In addition, you can also start with a C 3 temperature drop, and then maintain the temperature for a certain period of time before changing the temperature. The advantage of this approach is that a uniform thickness can be obtained. Therefore, when the temperature drop rate in the present invention is used together with the temperature reduction method, π is controlled to have a thickness of the stretch layer 2 3 and a uniform thickness can be obtained. The stretched layer μ water = the controlled and uniform thickness of the layer 23 makes the quantum layer uniform, and increases the monochromaticity and emission density of the emitted light. & As mentioned above, in this embodiment, in the light-emitting layer formed of indium-containing m group nitride and V body in a multi-phase structure, since the sub-phase system is mainly composed of having a stretch at the parent junction with the peripheral main phase Layer of crystals, so in the sub-phase

Page 13 V. Description of the invention (11) The surrounding stretching layer will stably generate carriers that increase the emission density. Therefore, a crystal constituting a sub-phase can be used as a quantized emission medium, and high-frequency visible light from a nitride semiconductor light-emitting device having this light-emitting layer can be stably emitted with a high density and excellent monochromaticity. Furthermore, since the sub-phase is mainly composed of a crystal having a stretched layer having a thickness of 5 x D4 or less, the thickness of the stretched layer can be maintained at a value capable of high-density emission. Furthermore, since the sub-phases having a stretched layer account for more than 50% of the total number of sub-phases, the enhancement of the emission density due to the characteristics of the stretched layer is reliable. Since the density of the sub-phase is set at 2x1018cnr3 or less, an emission light having excellent early color properties and having a thickness of half or less of 15 nm can be obtained. A specific example of the present invention will be described below. The present invention is not limited to the following examples. First Embodiment An application example of the present invention to a light emitting diode (LED) will be described below. The following steps are a process of sequentially forming a unit layer of the LED stacked layer structure on the two substrates by using an atmospheric pressure type secretion reactor.) ° Soil Figure 2 is a diagram showing the structure of a stacked layer according to the first embodiment of the present invention. The stacked layer 11 is composed of stacked unit layers on a substrate H0. ^ Bottom 100 is a 2 inch (50 cm) diameter of about 90 (000 1) (c-surface) -sapphire (α_Αΐ203 single crystal), all polished. An aluminum gallium nitride thin film is formed on the substrate 100 by using trimethylgallium, trimethylaluminum, and ammonia as raw materials through a normal pressure MOCVD method.

The low-temperature buffer layer 1 0 0 a. The film formation was performed in a hydrogen stream at 43 ° C for three minutes. The hydrogen flow rate was 8 liters per minute, and the ammonia gas flow rate was 1 liter per minute. The thickness of the low-temperature buffer layer is 5 nm. Next, hydrogen containing disilane (Si2H6) with a bulk density of about 3 ppm is added to a MOVCD reaction system, and an N-type gallium nitride (GaN) layer 101 will be at a low temperature after 90 minutes in a hydrogen-argon gas flow under iioirc. A buffer layer 100 & is formed. The amount of disilane-hydrogen mixed gas added to the system is precisely controlled by an electronic flow controller (MFC) at 10 cc per minute. The carrier concentration of the doped Shi Xi n-type gallium nitride layer 101 is 3 × 1018 cm-3, and its thickness is about 3 am.

The temperature on the substrate 100 is from 1100. (: After reducing to 8 0 ° C, a light-emitting layer composed of gallium indium nitride (Ga () 82lnQ 1βN) containing fl8%) is deposited on the N-type vaporized gallium layer 101. The formation of the light-emitting layer is performed in an argon gas stream. The thickness of the light-emitting layer 102 is 5 nm. The sources of gallium and gadolinium are trimethylgallium and trifluorenylindium. The trifluorenylgallium is maintained at a certain temperature. And the injected hydrogen is precisely controlled by MFC at 1 c · c. Per minute. The trifluorene indium is kept at a certain temperature of 50 ° C. The hydrogen flow rate with the sublimated trimethyl indium gas is controlled by the MFC It is set at 13c. C. Per minute. The flow rate of ammonia gas as a nitrogen source is set so that the ratio of V / ΠI is about 3 X 1 04 when the light emitting layer 102 is generated. Here, the ratio of ν / plate represents The ratio of the nitrogen source to the total concentration of gallium and indium sources supplied to the generation reaction system. The generation rate of the light-emitting layer is slower than that of the N-type gallium nitride layer 101 and is set to about 2 nm per minute. After the generation of the light-emitting layer 102 is completed After that, the substrate 100 rapidly rose from 800 ° to ^ (^^. In a stream of argon at a rate of 100 ° C per minute at -11 During the waiting time at 0 0 C, the mixed gas in the μ 〇 c V D reaction system

Page 15

It was replaced with a hydrogen-argon mixed gas, and a magnesium-doped aluminum-gallium nitride (AUao ^ N) mixed crystal layer 103 was formed on the light-emitting layer i02. The generation rate is about 3 nm per minute, which is 15 times the generation rate of the luminescent layer 102. This generation time continued for 10 minutes to obtain a mixed layer having a thickness of about 30 nm. The source of erbium is bis- (C5H5) 2Mg). Its supply rate is 8 x 10-6 m / min. The concentration of magnesium atoms in the magnesium-doped aluminum gallium nitride layer ˜03 was obtained by general SIMS analysis to be about 6 × 10 μ9 at 0 ms / cm3. Therefore, after 20 minutes in a hydrogen-argon mixed gas flow at 1100 ° C, a magnesium-doped gallium nitride layer 103a was deposited on the magnesium-doped aluminum gallium nitride layer 103. Dimethyl gallium was used as the gallium source, and the same magnesium organic compound as that used to form the magnesium doped gallium nitride layer 103 was used as the magnesium source. Since the doping efficiency of the lock increases as the generation rate decreases, the generation rate is set to about 3 nm per minute. The thickness of the magnesium-doped gallium nitride layer 103a is set at about 60 nm. After the unit layers 100a, 1002, 103, and 103afl of the stack layer structure 11 are formed, the temperature of the substrate 100 is added to the same volume of ammonia gas to a mixture containing argon and hydrogen. In the case of gas, immediately decrease from 丨 丨 〇〇 to 950 ° C. From 1100 ° C to 950 ° C, only hydrogen with a high thermal conductivity increased from 4 liters per minute to 8 liters per minute 'and the substrate was forced to cool within one minute. After the temperature of the substrate 100 dropped to 95 °, only argon gas flowed into the MOCVD reactor. From 950 t to 65 (rc is performed at a rate of 10 C per minute for 30 minutes. From 6 50. (: to room temperature is performed by using an argon and hydrogen gas mixture in a mCVD reactor) It takes 45 minutes to bring the temperature down to about 30 ° C.

Page 16 V. Explanation of the invention (14) Taking a part of the stacked layer structure 11 as an example, after cooling, the internal structure of the light emitting layer 102 is observed through a general cross-section TEM technique with an acceleration voltage of 2000 kV . Fig. 3 is a lattice image obtained by photographing the light-emitting layer of the nitride semiconductor light-emitting element of the first embodiment using an electron microscope. The magnification is 2 X 106. Fig. 3 shows that the light-emitting layer 102 in the first embodiment is composed of a multi-phase structure composed of a main phase 201 and a sub-phase 002 having an approximately spherical 戌 or island shape. Most of the island-shaped sub-phases 202 appear near the junction of the light-emitting layer 102 and the n-type gallium nitride layer 101. The density of the child phase 2 02 in the shooting range is about 2 X 1017 cm-3. The indium content of the main phase 201 and the sub-phase 202 is different 'and the indium concentration of the sub-phase 202 is higher than that of the main phase 201. The indium concentration of the subphase is about 30%. Each sub-phase 202 has a tensile layer at the interface with the main phase 2 01. The diameter of the sub-phase 202, which is approximately spherical, is approximately 25 Angstroms to 35 Angstroms. (2.5 nm to 3.5 nm). The width of the island-shaped child phase 202 is about 35 Angstroms. In some cases, the difference between the deflection angle of the lattice plane of the sub-phase 202 and the stretched 203 is about 60. . Although the stretched layer 203 does not always maintain the same thickness around the sub-phase 202, its average thickness is about 0 Angstroms. The thickness d of the stretched layer 20 3 around the sub-phase 2002 having a diameter or width between 25 and 35 angstroms is about 8 angstroms to 13 angstroms. The thickness d of the stretched layer 203 around the sub-phase 2/2 has a relatively small straight or width of 5 to 7 angstroms. In addition, the sub-phase of the stretched layer with this thickness accounts for about 86%. 〇 LEDs are manufactured using the above-mentioned stacked layer structure as a material.

Page 17 FIG. 4 is a cross-sectional view of the LED in the first embodiment. This cross section is obtained from line 4-4 in FIG. Figure 5 is a plan view of the LED. LED 50 is obtained by adding electrodes to the above-mentioned stacked layer structure. First, a plasma-etching process is performed using a methane / argon / hydrogen mixed gas to form a shaped region of the electrode 109. The N-type electrode 9 is formed on the surface portion of the gallium nitride layer 100 by etching by a general vacuum evaporation method, and is formed of 1 " 〇〇_ and is composed of pure aluminum. A p-type electrode is formed on the f-doped gallium nitride layer 103 (that is, the uppermost surface layer of the platform structure) by a general vacuum evaporation method. The surface of the electrode 105 that is doped with Mg = contact is made of a gold-beryllium alloy, while the other surface is made of pure gold. The thickness of the electrode 105 is about 2emQp-type electrode 105 is located above the LED, a surface layer, and at a corner portion of the opposite side of the N-type electrode 1009. A transparent gold box electrode of two thicknesses of 20 nm is located on the surface of the magnesium-doped gallium nitride layer 103a to make electrical contact with the p-type electrode 105. Furthermore, a nickel oxide thin film electrode 10 having a thickness of two, a wide moon, and a f edge is formed on the surface of the gold pig. Thin ㈣4a is used as a protective film on the exposed surface of the entire gold box electrode iQ4 and the doped GaN layer 103a. The LED 50 can emit light by adding between the N-type electrode 109 and the 13-type electrode 105. Table 1 lists the measured emission characteristics. In forming the cooling conditions of the first embodiment described above, in particular, the cooling conditions of the first embodiment are different. After the stacked layer structure i in the embodiment, the structure was cooled under different conditions from the embodiment of the same embodiment under the same conditions as in Example 1. After the temperature was reduced from 1 1 000 C to 5, the description of the invention (16) 950 ° C, After 20 minutes at a speed of 7.5 ° C per minute, the temperature was lowered from 95 ° t to 80 °. (:. Then, the temperature was fixed at 800 ° C for 15 minutes. Then, the temperature was reduced from 800 ° C to 65 ° C at a rate of 10 ° C per minute. At a temperature of 650 ° After C, only the hydrogen gas is allowed to enter the MOCVD reactor, and the temperature is reduced to room temperature. It takes about 45 minutes to cool to 30 ° C. After cooling, the internal structure of the light-emitting layer can be found by cross-section TEM technology. The light-emitting layer of the second embodiment has a multi-phase structure composed of a main phase and a sub-phase, similar to the light-emitting layer 10 of the first embodiment. The sub-phase has a stretch layer at the interface with the main phase. The sub-phase The indium concentration is usually higher than that of the main phase, and the copper phase of the main phase is about 0.15. The subphases are mainly ...- approximately spherical bodies with a uniform diameter of 30 angstroms. In addition, the pulls around the subphases are approximately g The thickness of the stretched layer is 10 Angstroms. As mentioned above, in the second embodiment, the cooling process of the temperature includes the step of fixing the temperature at 800 for 15 minutes. The shape of the J phase can be approximately spherical and stretched. The thickness is also transmitted uniformly by this 79C. Furthermore, the Comparative Example division ratio of gas down about ii- embodiment embodiment of the stacked-layer structure is formed, the temperature of the natural discipline. Temperature was reduced to 3 "C in about 90 minutes. Thus, the average Pan

9 Master clock 12 ° c. According to the conventional technology (refer to the Japanese Patent Publication No.), the second embodiment of the gas system 1Qm is different in that after 65 (rc after two: two and 。. 俛 亚, there is only the horizontal passage of hydrogen Section TEM technology can be observed under the above-mentioned traditional cooling conditions

Page 19 5. Description of the invention (17) The internal structure of the light-emitting layer of the stacked layer structure cooled down. Although you can see the linear black image of J due to distortion, you can't see the spherical or island image of the subphase caused by the indium I set. From the number of spherical and island-shaped shirt images in the captured images, the density of the sub-phases is (χ 1 0〗 2 cm-3 or less. In particular, the light-emitting layer cannot be clearly seen to be formed by a multi-phase structure. Tian was cooled under the cooling conditions of the first embodiment and the comparative example, and the layered structure was processed in the same manner as in the first embodiment to produce [M. Each LED was applied with a DC voltage between its electrodes. Instead, the measured emission characteristics are listed in Table 1.

The emission wavelengths in the table are compared with the comparative examples. The emission wavelengths are not significant. '1 The first and second emission characteristics are compared. There is also no significant difference between the positive and negative bias voltages between 430 and 450 nm. But on the other hand, in the force-II emission density, the second implementation with a maximum value of 20%, which is an example obtained by measuring with a volume component of approximately ==, is the smallest, which is 0.4nw. The emission density of the LED in the main emission example is known that the half-width of the radio frequency (FWHM) has a significant difference &

-1¾. 87121: _correction 5 Description of the invention Different. The first example 7nm is f 丨 Chu T ~ Z ~ 'H, the example 18_ is the maximum. The ratio is the smallest, and the example is 9 nm, which is comparatively implemented. Although the present invention has been described, the fLED ’s emitted light lacks monochromaticity. It is not used to limit the preferred embodiment to reveal such as the scope of the spiritual toilet, and anyone who knows this technology can make some modifications and modifications without departing from the second example of the present invention. The scope of this month shall be subject to the scope of patent application attached. Description of this wool symbol: 2, 10 ~ 2 light-emitting layer; u ~ stacked layer; 21, 2 (n ~ main phase; 22, bit; 23 ~ stretch layer; 50 ~ LED; 100 ~ substrate; 100 & low temperature, -f_a, 10 1 ~ N-type gallium nitride layer; 1 03 ~ mixed crystal layer; 103 g ~ gallium nitride layer, 104 ~ gold foil electrode; i 04a ~ nickel oxide thin film electrode; 105 ~ p type electrode; 109 ~ N type electrode; 203 ~ stretched layer.

Sixth, the scope of patent application 1. A nitride semi-conductor semiconductor layer as a multi-phase multi-phase indium content indium content 'special component of the device' the crystal and the main phase 2. If the patent application features The width of these sub-phases is 0.5x D or shorter. 3. If the patent application is characterized by the range of the stretched layer.

Number 87121RM

Conductive light-emitting element, ϊ1 indium-containing m-group nitrided light layer, the semiconductor layer is composed of a main phase and a complex structure, and the main phase and the sub-phases have different characteristics because the sub-phases are mainly composed of crystals. The boundary of the structure is surrounded by a stretched layer. The element described in item 1, wherein the element is mainly composed of a crystal, and the crystal has a stretched layer 'D which represents the full width of the subphase. The element described in item 1, wherein the thickness of one of the elements is one of between 5 angstroms and 10 nm. 4 · The element described in claim 1, 2 or 3 of the patent scope, wherein It is characterized in that the number of the sub-phases having the stretched layer accounts for more than 50% of the total number of the phases. _ 5. The element according to item 1, 2 or 3 of the scope of patent application, wherein the element is characterized in that one of the sub-phases has a density of 2〆10 cm 3 or less. 6. The element according to item 1, 2, or 3 of the scope of patent application, wherein the element is characterized in that one of the light emitting layers has a thickness between ΐηη and 300nm.

7. A nitride semiconductor light-emitting device ^ manufacturing method 'The device uses a steel-containing group III nitride semiconductor layer as a light-emitting layer, wherein the semiconductor layer is a multi-phase structure composed of a main phase and a plurality of sub-phases And the main phase and the nettle phase have different indium contents, the method is characterized by the following steps: z The light-emitting layer is heat-treated at a heat treatment temperature, and the heat treatment

2000. 04.18. 022 _ Case No. 87121669 6. The scope of the patent application is that the correction temperature is between 95 and 120 ° C; the light-emitting layer is removed from the heat treatment temperature at a rate of more than 20 ° C per minute. Cool to 9 50 ° C; cool the light-emitting layer from 9 50 ° C to 6 50 ° C at a speed below 20 ° C per minute, and at the junction of the main phase and the sub-phases Forms plural stretched zhan. 8. The method according to item 7 of the scope of patent application, wherein the method is characterized in that the light-emitting layer is placed at any temperature between 9 50 ° C and 6 50 ° C during cooling from the heat treatment temperature. A preset time at a temperature.

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