TWI304275B - Gallium nitride-based compound semiconductor multilayer structure and production method thereof - Google Patents

Description

1304275 IX. Description of the Invention: [Technical Field] The present invention relates to a gallium nitride-based compound semiconductor laminate useful for the production of a light-emitting element that emits light in a blue, green or ultraviolet region with high output and System of law. [Prior Art] In recent years, a nitride semiconductor material has been attracting attention as a semiconductor material for a light-emitting element that emits light of a short wavelength. In general, a nitride semiconductor B system uses a variety of oxide crystals, single crystals of tantalum carbide, and single crystals of a III-V compound semiconductor, including sapphire single crystals, as a substrate, and an organic metal vapor phase chemical reaction method thereon. (MOCVD method), molecular line epitaxial growth method (ΜBE method) or hydride vapor phase epitaxial growth method (HVPE method) or the like is laminated. At present, the most widely used crystal growth method in the industrial grade is a method in which sapphire, SiC, GaN, A1N, or the like is used as a substrate, and a method in which an organometallic vapor phase chemical reaction method (MOCVD method) is used, B The group III organometallic compound and the group V source gas are used in the reaction tube in which the substrate is provided, and the n-type layer, the light-emitting layer, and the ruthenium-type layer are grown in a region of a temperature of 700 ° C to 1 200 ° C. After the growth of each semiconductor layer, a positive electrode is formed on the ruthenium-type layer by forming a negative electrode due to the substrate or the n-type layer, and a light-emitting element can be obtained. Conventional light-emitting layer, in order to adjust the wavelength of light, use the adjusted composition

In GaN, and a multi-quantum well structure in which a double-heterostructure with a high band gap is sandwiched by InGaN and a quantum well effect is used. 1304275 In a gallium nitride-based compound semiconductor light-emitting device having a light-emitting layer of a multiple quantum well structure, when the film thickness of the well layer is 2 to 3 nm, a good output can be obtained. However, there is a problem of high driving voltage. On the other hand, when the film thickness of the well layer is 2 nm or less, although the driving voltage is lowered, a good output cannot be obtained. Further, in order to increase the light-emitting output, a quantum dot structure in which the light-emitting layer is formed into a dot shape is proposed as follows. For example, a light-emitting element having a light-emitting layer including a quantum dot structure is disclosed in Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. The surface active effect is formed. According to Japanese Laid-Open Patent Publication No. Hei No. Hei 1 1 - 3 548 399, the size of each illuminant is preferably 〇5 nm$ height S50 nm, 0.5 nm width S200 nm, 106$ density S1 〇 13 cm·2, in the embodiment, It is made of a height of 6 nm x a width of 40 nm. However, in addition to the portion covered by the quantum dots, it is an extremely low-low resistance region as compared with the dot region, and the current is preferentially flowed, and the non-dot portion does not contribute to the light emission. As a result, in the quantum dot structure B proposed herein, even if the luminous efficiency of each of the luminous bodies can be improved, there is a problem that the luminous output of the flowing current is lowered as a whole. Further, Japanese Patent Publication No. 200 687 333 discloses a quantum box structure including In. According to this publication, a quantum box structure is formed by annealing a temporarily formed quantum well in hydrogen gas to cause sublimation of the well layer. In an embodiment, the quantum box has a size of 200 angstroms or less, for example, having a size of 20 angstroms x 20 angstroms x 20 angstroms. Although the density of the illuminant is not specified, according to the disclosed surface, the area covered by the illuminant is the same as the area of the gap of 1304275 or the gap is large. In short, in these technologies, in a region where quantum dots or quantum boxes are not formed, a structure in which dots or boxes are not formed at all is formed, and therefore, compared with a region in which quantum dots or quantum boxes are formed, Extremely low and low resistance area, and current flows preferentially in this part. In the structure in which the illuminant is not formed in the uncovered region of such a dot or box, the effect of lowering the driving voltage can be seen, but at the same time, there is a problem that the illuminating output is lowered, and it is not suitable for practical use. Further, in Japanese Laid-Open Patent Publication No. 2001-68733, after forming a normal quantum well structure, annealing is performed in hydrogen gas to decompose the InGaN crystals in the transposition to form a quantum box structure. However, the quantum well structure is annealed in hydrogen gas, and even if a part of the quantum box structure is formed to remain, the detachment of In is induced, and an unfavorable situation is caused in which the emission wavelength is shortened. In order to obtain high-efficiency luminescence, a luminescent layer of a multiple quantum well structure having a variation in film thickness in a well layer is proposed in the specification of U.S. Patent Application Publication No. 2003/0 1 60229 A1. In this specification, the deviation of the film thickness is set in the whole well layer in the range seen in the attached panel. SUMMARY OF THE INVENTION An object of the present invention is to provide a gallium nitride-based compound semiconductor laminate which is useful for the production of a gallium nitride-based compound semiconductor light-emitting device which can reduce a driving voltage and has a good light-emitting output. The present invention provides the following invention. (1) A gallium nitride-based compound semiconductor laminate having an n-type layer, a light-emitting layer, and a p-type layer on a substrate; the light-emitting layer is interlaced with a multiple quantum structure in which a layer of a well layer and a barrier layer 1304275' are stacked, And the light-emitting layer is configured to be held by the n-type layer and the Ρ-type layer, and is characterized in that: the well layer constituting the multiple quantum structure is a well layer with uneven thickness and a well layer with uniform thickness Composition. (2) The gallium nitride-based compound semiconductor laminate according to the above item 1, wherein the well layer closest to the ruthenium layer has a uniform thickness. (3) The gallium nitride-based compound semiconductor laminate according to the above item 1, wherein the well layer closest to the n-type layer has a uniform thickness. (4) The gallium nitride-based compound semiconductor ® laminate according to any one of items 1 to 3 above, wherein the thickness of the well layer having a uniform thickness is 1.8 to 5 nm. (5) The gallium nitride-based compound semiconductor laminate according to any one of the items 1 to 4, wherein the film thickness of the thin film portion of the well layer having a thickness unevenness is 2.7 nm or less. (6) The gallium nitride-based compound semiconductor laminate according to any one of items 1 to 5 above, wherein the multiple quantum well structure has a structure in which the well layer and the barrier layer are formed by 3 to 10 times. (7) The gallium nitride-based compound semiconductor laminate according to any one of items 1 to 6, wherein the barrier layer is formed from a group of InGaN having a ratio of In which is smaller than InGaN forming GaN, AlGaN, and a well layer. A gallium nitride-based compound semiconductor is selected. (8) The gallium nitride-based compound semiconductor laminate of the above item 7, wherein the barrier layer is GaN. (9) The gallium nitride-based compound semiconductor laminate according to any one of the items 1 to 8, wherein the barrier layer is a dopant. (10) The gallium nitride-based compound semiconductor laminate according to the above item 9, wherein the dopant in 1304275 is from C, Si, Ge, Sn 'Pb, 〇, S, Se, Te, Po, Be, Mg, At least one selected from the group consisting of Ca, Sr, Ba, and Ra. (1) A gallium nitride-based compound semiconductor laminate according to the above item 9 or 10, wherein the concentration of the dopant is 1 X 1 〇 17 c π Γ 3 to 1 X 1 〇 18 c η Γ 3. The gallium nitride-based compound semiconductive volume layer according to any one of the above items 1 to 11, wherein the barrier layer has a film thickness of 7 to 50 nm. (1) The gallium nitride-based compound semiconductor laminate of the above item 1, wherein the barrier layer has a film thickness of 14 nm or more. (1) The gallium nitride-based compound semi-volume layer of any one of the above items 1 to 3, wherein the well layer contains In. (1) The gallium nitride-based compound semiconductor laminate according to the above item 14, wherein a thin layer not containing In is present on at least the substrate side surface of the barrier layer. (16) A forbearing grafting compound semiconductor light-emitting device, characterized in that: the n-type layer of the gallium nitride-based compound semiconductor laminate according to any one of the above items 1 to 5 is provided with a negative electrode, and is p-type The layer is set to the positive pole. (17) A lamp used in which the gallium nitride-based compound semiconductor light-emitting device of the above-mentioned item 16. (18) A method for producing a gallium nitride-based compound rich volume layer according to any one of the above items (15), characterized in that, after forming a well layer, by making the part of the well layer Decompose or sublimate to form a well layer with uneven thickness. (19) The method for producing a gallium nitride-based compound semiconductor laminate according to the above item 18, wherein a substrate temperature Τ 1 when the well layer is formed and a substrate temperature Τ 2 when the portion of the well layer is decomposed or sublimated are Ϊ́ΐ$Τ2. The method for producing a gallium nitride-based compound semiconductor layer according to the above item 18 or 19, wherein the decomposition or sublimation of the portion of the well layer is contained in a nitrogen source and is not contained The Group III metal source is operated under a gaseous environment. (2) The method for producing a gallium nitride-based compound semiconductor laminate according to any one of the above-mentioned items 18 to 20, wherein the decomposition or sublimation of the portion of the well layer is performed in the step of forming the barrier layer . The main structure of the present invention is to mix a well layer having a non-uniform thickness and a well layer having a uniform thickness in a well-layered layer of a multi-layer quantum structure forming a light-emitting layer, and the root B can obtain a good light-emitting output according to the present invention. Further, the gallium nitride-based compound semiconductor light-emitting device can reduce the driving voltage. Further, the gallium nitride-based compound semiconductor light-emitting device obtained according to the present invention has less deterioration in the reverse direction withstand voltage characteristics. Further, by forming a well layer having a thickness unevenness in the presence of a nitrogen source, it is possible to prevent the short-wavelength of light generated from the well layer. [Embodiment] It is known that a gallium nitride-based compound semiconductor constituting an n-type layer, a luminescent layer, and a bismuth layer of a gallium nitride-based compound semiconductor light-emitting device is of the general formula AlxInyGai-x.yN (0Sx<1, 〇 $y<1, 〇Sx + y<1) A semiconductor of various compositions represented by the present invention, and the gallium nitride-based compound semiconductor constituting the n-type layer, the light-emitting layer, and the bismuth layer of the present invention can be used without any limitation A semiconductor of various compositions represented by the general formula AlxInyGai-x-yN (0S x < 1, 〇$ y < 1, OS x + y < 1). As the substrate, a conventionally known substrate such as GaP, GaAs, Si, Zn or GaN can be used without any limitation except for using sapphire or SiC. -10- 1304275 In addition to the GaN substrate, in principle, in order to laminate a gallium nitride-based compound semiconductor on the substrates which are not lattice-integrated with the gallium nitride-based compound, Japanese Patent No. 3026087, A lattice unconformed crystal epitaxial growth technique called SP (Seeding Process), which is disclosed in Japanese Laid-Open Patent Publication No. H03-243302, and the like. In particular, the S P method for producing an A1N crystal film at a high temperature to the extent that GaN-based crystals can be produced is a lattice inhomogeneous crystal epitaxial growth technique which is excellent in terms of productivity and the like. In the case of using a lattice unconformed crystal epitaxial growth technique such as a low-temperature buffer method or an SP method, a gallium nitride-based compound semiconductor laminated thereon as a substrate is undoped or low in the range of 5×1 017 cm·3. Doped GaN is preferred. The film thickness of the substrate layer is preferably from 1 to 20 // m, more preferably from 5 to 15 // m. An n-type layer, a light-emitting layer, and a p-type layer are sequentially laminated thereon. In the present invention, the well layer of the multilayer quantum structure forming the light-emitting layer is required to mix the well layer having a uniform thickness and the well layer having a small thickness. In the present invention, "even thickness" means that the film thickness falls within ±10% of the average film thickness at any point. Among them, it is preferable to fall within ±7 %. "Uneven thickness" means a portion having a film thickness that does not fall within ±10% of the average film thickness. The "average film thickness" means the film thickness calculated by averaging the maximum film thickness and the minimum film thickness of the film. In the well layer having uneven thickness, a portion thicker than the average film thickness is referred to as a "thick film portion", and a portion called a thin portion is a "thin film portion". Whether the thickness of each of the well layers is uniform or uneven can be determined and measured by a cross-sectional ΤΕΜ photograph of the gallium nitride-based compound semiconductor. For example, when the cross-section is observed from 200,000 to 2,000,000 times of ΤΕΜ photos, the film thickness of each well layer can be measured -11 - 1304275 '. The third to tenth figures show the film thickness by the cross-sectional TEM photograph of the magnification of 1,000,000 times the wafer produced by the first method, and the magnification. The maximum film thickness and minimum film thickness of each well layer in the table attached to the side of each figure are attached. The maximum film thickness and the minimum film thickness of each well layer obtained from the eight figures are the well-thickness of the well layer or the uneven thickness of the well calculated by the average calculation of the maximum film thickness and the minimum film thickness. The average film thickness is divided into a thick film portion, and the thinner portion is a thin film portion. In the figure, A is ® B for the film portion. The maximum film thickness and the minimum film thickness of each well layer are obtained by observing at least 8 locations of the TEM facets, for example, at least 8 intervals from the adjacent spaces. In the case of unevenness in all wells in the multiple quantum well structure in which the light-emitting layer is formed, and in the case where the thickness is uniform in all the well layers, although the driving voltage is lowered, the light-emitting output is also decreased or the same. When the thickness of all the well layers is not made uneven, and the well layer is made uniform, although the reason is not sufficiently understood, the dynamic voltage is lowered and the luminous output is increased. In particular, in the case where the thickness of the well layer of the outermost layer or the η-type layer is uniform, the light-emitting effect is large. In the case where the thickness of both the well layer closest to the p-type layer and the most well-layered well layer is uniform, the luminous output effect is maximized, but the driving voltage reduction effect is also reduced. A well-balanced well layer' may include both wells closest to the p-type layer being close to the n-type layer of the well layer, but including one of the well layers having a uniform thickness, especially including the closest p-type Layer 1 embodiment piece. Can test, record the combination of these, can determine the household level. Compared with the thicker part of the film, it is possible to use the 20 μm layer to compare the thickness. However, when one part has the increase of the near-P-type output, the increase is close to the η-type. Therefore, the thick layer And most preferred. It is better to use the well floor 1304275. - When the number of wells with a uniform thickness increases, the effect of reducing the drive voltage will be reduced by >. Therefore, it is preferable that the number of well layers having a uniform thickness is 1 or more and 60% or less of the total number of the well layers. In particular, less than 40% of the total number of wells is preferred. It is preferred that the thickness of the well layer having a uniform thickness is 1.8 to 5 nm. When it is outside the range, it will cause a decrease in the light output. More preferably, it is in the range of 2.0 to 3.5 nm. > It is preferable that the thickness of the thick film portion of the well layer having a small thickness is 1.8 to 5 nm. When the thick film portion is outside the range, the light output is lowered. More preferably in the range of 2.3 to 3.5 nm. Further, it is preferable that the thickness of the thick film portion is 10 to 5000 nm. More preferably 20~lOOOnm. It is preferable that the ratio of the thick film portion is 30 to 90% with respect to the entire well layer, which can achieve both a reduction in driving voltage and an increase in output. More preferably 60 to 90%. The ratio of the thick film portion to the thin film portion can also be calculated from the measurement 値 of the width obtained from the cross-sectional TEM photograph. It is preferable that the width of the thin 0 portion is 1 to 200 nm. More preferably, it is 5 to 150 nm. It is preferable that the difference between the maximum film thickness of the thick film portion and the minimum film thickness of the thin film portion is about 1 to 3 nm. The film thickness of the film portion is preferably i.o to 27 nm. The thin film portion may include a range in which the film thickness is zero, that is, a range in which the well-free layer is completely omitted. However, since the light output is lowered, it is preferable that the film portion has a small range. The overall well layer is preferably 30% or less, more preferably 20% or less, and more preferably 1% or less. This ratio can be calculated from the measurement of the width of the cross-sectional TEM photograph -13 - 1304275. The well layer is preferably a gallium nitride-based compound semiconductor containing In. The gallium nitride-based compound semiconductor containing In is likely to be a crystal system having a structure of a thick film portion and a thin film portion, and can emit light in a wavelength region of blue light with strong luminescence intensity. In addition to GaN or AlGaN, the barrier layer may be formed of InGaN having a smaller In ratio than the InGaN constituting the well layer. Among them, GaN is more suitable. The barrier layer may also be a multi-layered construction. In the case where the well layer is a gallium nitride-based compound semiconductor containing In, it is preferable to provide a thin layer not containing In on the surface of the barrier layer which is at least in contact with the well layer on the substrate side. It is preferable to suppress the decomposition and sublimation of In in the well layer by providing the thin layer, so that stable control of the emission wavelength is possible. The thin layer is preferably set to a substrate temperature which is the same as the growth temperature of the well layer. When a dopant is doped into the barrier layer, the driving voltage is lowered to be preferable. Examples of the dopant element include C, Si, Ge, Sn, Pb, yttrium, S, Se, Te, Po, Be, Mg, Ca, Sr, Ba, Ra, and the like. Among them, Si and Ge are preferred, and Si is particularly preferred. The concentration of the dopant is preferably 5xl016cm_3~lxl018cm.3. If it is less than 5x10 16cnT3, the effect of reducing the driving voltage will be reduced. When it exceeds lxl018cirT3, the reverse voltage characteristic tends to be deteriorated. More preferably lxl017cm_3 ~ 5xl 〇 17cm_3. The film thickness of the barrier layer is preferably 7 n m or more, and more preferably 1 4 n m or more. When the film thickness of the barrier layer is thin, the thickness difference between the thick film portion and the film portion of the well layer cannot be completely filled, which hinders the formation of the thick film portion of the well layer and the film-14-8' 1304275 portion, thereby causing A decrease in luminous efficiency and a decrease in aging characteristics. • In addition, when the film thickness of the barrier layer is too thick, the driving voltage is increased and the light output is lowered. Therefore, the film thickness of the barrier layer is preferably 50 nm or less. The number of layers of the multiple two-well structure is preferably 3 to 10 times, more preferably 3 to 6 times. In each of the well layers and the barrier layer, the composition and structure can also be changed. The n-type layer is usually 1 to 10 / / m, preferably 2 to 5 / / m, and the n-contact layer for forming a negative electrode and the band gap are larger than the light-emitting layer and are in contact with the light-emitting layer. The cover layer is composed of. The η contact layer and the η coating layer may also be used in combination. It is preferred that the η contact layer is doped with Si or Ge at a high concentration. It is preferable to dope the n-type layer formed by the dopants so as to adjust the carrier concentration to 5x1OI8cm·3 to 2xl019cnT3. The η coating layer may be formed of AlGaN, GaN, InGaN or the like. However, in the case of InGaN, it is preferable to form a composition having a larger band gap than InGaN of the light-emitting layer. The carrier concentration of the η coating layer can be the same as that of the n contact layer, and ® can be larger or smaller than it. In order to further improve the crystallinity of the light-emitting layer formed thereon, it is preferred to form a surface having a high flatness by appropriately adjusting growth conditions such as growth rate, growth temperature, growth pressure, and doping amount. Further, the η coating layer may be formed by a layer having a laminated composition and a lattice constant differently. At this time, in addition to changing the composition by the layer of the layer, the amount of the dopant, the film thickness, and the like can be changed. The ruthenium layer is usually a thickness of 0.01 to 1/m, and is composed of a P-coat layer which is in contact with the light-emitting layer and a P-contact layer which forms a positive electrode. The p-coat layer and the p-contact 1304275 touch layer can also be used. The P-cladding layer is formed using GaN, AlGaN, or the like, and 'doped Mg' as a p-dopant. In order to prevent excessive flow of electrons, it is preferable to form a material having a band gap larger than that of the material of the light-emitting layer. Further, it is preferable to form a layer having a high carrier concentration in such a manner that the carrier can be efficiently injected into the light-emitting layer. The P-cladding layer can also be formed by using a layer having a plurality of layers and a different lattice constant. At this time, in addition to changing the composition by the layer of the layer, the amount of the dopant, the film thickness, and the like can be changed. The t P contact layer can be formed using GaN, AlGaN, In GaN, or the like, and doped

Mg acts as an impurity. The gallium nitride-based compound semiconductor doped with Mg is usually high-resistance in the original state taken out from the reaction furnace, but is subjected to an activation treatment such as annealing treatment, electron beam irradiation treatment, or microwave irradiation treatment to display P conduction. Sex. Alternatively, boron phosphide doped with a P-type impurity may be used as the P-contact layer. Phosphorus phosphide doped with a P-type impurity exhibits P conductivity even if the treatment for P-type as described above is not performed at all. The method for growing the gallium nitride-based compound semiconductor constituting the n-type layer, the light-emitting layer, and the p-type layer is not particularly limited, and known methods such as ruthenium, MOCVD, and HVPE can be used under known conditions. Among them, the MOCVD method is preferred. Ammonia, hydrazine, azide, or the like can be used as the raw material. Further, potassium trichloride (TMGa), triethylpotassium (TEGa), trimethylindium (TMIn), trimethylaluminum (ΤΜΑ1) or the like can be used as the group III organic metal. Further, as a doping source, decane, acetane, brothel, organic ruthenium raw material, dicyclopentadienyl magnesium (Cp2Mg), other organometallic-16- • 1304275 type, hydride or the like can be used. Nitrogen and hydrogen can be used to carry the gas. The well layer having a non-uniform thickness is preferably formed by causing a portion of the well layer to be decomposed or sublimated after it has been grown to a specified thickness. The gallium nitride-based compound semiconductor containing In is preferred because it is easily decomposed or sublimated. The growth of the well layer containing In is preferably carried out at a substrate temperature of 650 to 900 °C. At the temperature below, the well layer having good crystallinity cannot be obtained, and at the temperature above, the amount of In taken into the well layer is reduced, and there is a case where it is impossible to produce an element that emits light at an intended wavelength. After supplying a group of metal containing a source of In and a source of nitrogen to one side, a well layer composed of a gallium nitride-based compound semiconductor containing In is grown to a predetermined thickness, and then the supply of the group III metal source is stopped. A part of the substrate can be decomposed or sublimated by maintaining the substrate temperature at the original temperature or increasing the temperature. The carrier gas system is preferably nitrogen. Decomposition or sublimation is preferably carried out by raising the temperature of the substrate from the growth temperature to a range of 700 to 1 000 °C or while raising the temperature. The growth of the barrier layer is preferably performed at a higher substrate temperature than the growth of the well layer. The temperature region is suitably 700 to 1 000 °C, and when the temperature at which the well layer is grown is T1 and the temperature at which the barrier layer is grown is T2, then T1 S T2. After the growth of the well layer, the step of stopping the supply of the group III raw material by the supply of the carrier gas and the nitrogen source containing the nitrogen gas from the temperature rising process of T1 to T2 can effectively form the thick layer in the well layer. The film portion and the film portion can be formed into a well layer having a non-uniform thickness. At this time, it is not necessary to change the carrier gas or the like. By switching the carrier gas to hydrogen and oxygen, the emission wavelength can be shortened. The degree of change in wavelength is difficult to control, so the production of the product is reduced to 1304275. ‘ The temperature increase rate from T1 to T2 is preferably 1 to 200 ° C /. Further, it is preferably 5. 5 / TC (TC / is divided. Further, the time required for the temperature rise from T1 to T2 is preferably 30 seconds to 10 minutes, more preferably 1 minute to 5 minutes. The growth can be carried out in a plurality of steps having different growth temperatures. That is, after the barrier layer is formed to a predetermined thickness on the well layer at a temperature of T2, the growth temperature can be further increased as a T3 layer. When T3 is a temperature lower than T2, it is preferable to provide an effect of suppressing degradation of aging characteristics, etc., and T3 may be the same temperature as T1. Further, as described above, in the well layer containing In In the case where a thin layer containing no In is provided on the substrate side surface of the barrier layer, in this case, after the well layer composed of the gallium nitride-based compound semiconductor containing In is grown at the temperature T 1 , In addition, the supply of the In source may be stopped at the same substrate temperature, and the barrier layer made of the gallium nitride-based compound semiconductor may be first grown at the temperature T1. The negative electrode is known to have various compositions and structures. ^ These well-known negative electrodes are used in the system. Contact layer with η In addition to Al, Ti, Ni, Au, etc., Cr, W, V, etc. may be used as the contact material for the negative electrode. The entire negative electrode may have a multilayer structure and may be provided with a lap bond property or the like. The positive electrode of various compositions and structures can be used without any limitation. The light-transmitting positive electrode material may include pt, pd, A u, C r, N i, C u, C 〇, etc. It is known that a structure which is partially oxidized can be used to improve light transmittance. A reflective type positive electrode material can be used in addition to the above materials, Rh, -18-.1304275

Ag, A1, etc. • These positive electrodes can be formed by methods such as sputtering, vacuum evaporation, and the like. In particular, when the sputtering method is used, it is preferable to obtain an ohmic contact after forming the electrode film without performing annealing treatment by appropriately controlling the conditions of the sputtering. The structure of the light-emitting element may be a flip-chip type element having a reflective positive electrode, or may be a face-up type element having a light-transmitting positive electrode, a lattice type, and a comb-type positive electrode. In the well layer having the thick film portion and the thickness of the thin film portion, the interface between the well layer and the barrier layer having different materials is inclined with respect to the substrate surface in the boundary region from the thick B film portion to the thin film portion, so The amount of light taken out in the direction perpendicular to the substrate surface is increased, and in particular, by forming a flip-chip type element structure including the reflective electrode, the light emission intensity can be further increased. By using the gallium nitride-based compound semiconductor laminate of the present invention, the driving voltage can be freely lowered to some extent. However, if the voltage drops too much, you will see a decrease in the luminous output. The driving voltage at which the light output is not lowered is preferably a voltage of B 2 · 5 V or more, more preferably 2 · 9 V or more, when a current of 20 mA flows when the element is formed. However, when the device is incorporated, the voltage is too high, which is disadvantageous, so it needs to be less than 3.5 V. The effect of using the gallium nitride-based compound semiconductor laminate of the present invention is a case where the current and the voltage which are one of the characteristics of the diode are related to each other, and the traction voltage in which the current is relatively increased with respect to the voltage is lowered. However, the relevant traction voltage is also such that if the drop is too much, the luminous output is reduced. The traction voltage which does not cause a decrease in the light-emitting output is preferably a voltage of 2.3 V or more when flowing a current of S) -19 - 1304275 2 0 mA when the component is formed, and more preferably 2.5 V or more. However, when the device is incorporated, the voltage is too high, which is disadvantageous, so it needs to be 3.4V or less at the same time. The gallium nitride-based compound semiconductor laminate of the present invention can be used for production of a light-emitting diode, a laser diode, or the like. A semiconductor light-emitting device is produced from the gallium nitride-based compound semiconductor laminate of the present invention. For example, a transparent cover can be provided by a means known in the art to produce a lamp. Further, a combination of the gallium nitride-based compound semiconductor light-emitting device of the present invention and a cover having a phosphor can also produce a white light lamp. Further, a gallium nitride-based compound semiconductor light-emitting device having high luminous intensity can be obtained. According to this method, a high-intensity LED lamp can be manufactured. Furthermore, an electronic device such as a mobile phone, a display, a panel, or the like incorporated in a wafer produced by the method, a mechanical device such as a car, a computer, or a game machine incorporated in the electronic device can be incorporated, and low-power driving can be achieved. Achieve high features. In particular, in battery-operated devices such as mobile phones, game consoles, and automobile parts, power saving effects can be achieved. (Embodiment) Next, the present invention will be described in detail based on examples, but the present invention is not limited by the examples. (First Embodiment) Fig. 1 is a schematic view showing a gallium nitride-based compound semiconductor laminate for a semiconductor device produced in the present embodiment (however, the well layer and the barrier layer of the light-emitting layer are omitted). As shown in Fig. 1, on the sapphire substrate having a C-plane, a layer of -20-1304275 to s P composed of A1N is laminated by an epitaxial growth method of lattice unconformity crystallization, and on the substrate side from above An undoped GaN substrate layer having a thickness of 8 // m, a highly doped Ge-type n-type GaN contact layer having an electron concentration of about 1×10 019 T3 and a thickness of 2/zm, having an ixi〇i8 cm·3 layer The Si-doped n-type 111 having an electron concentration and a thickness of 20 nm. .〇2〇3. The .98 coating layer, a 6-layer layer of a 3xl017cm·3 doped Si GaN barrier layer having a thickness of 15 nm, and 5 layers of an undoped In 〇.〇 8Ga having a thickness of 3 nm. .9 A light-emitting layer of a multi-quantum well structure composed of a well layer composed of a thin layer of 2N, a p-doped Mg-type ρ-type Al0.05Ga0.95N coating layer having a thickness of 16 nm, and a hole having 8xl017cm·3 B The concentration of the 0.2 m thick doped Mg p-type Al〇.〇2Ga〇.98N contact layer structure. The gallium nitride-based compound semiconductor laminate was produced by the MOCVD method in the following procedure. First, a sapphire substrate is introduced into a stainless steel reactor which can process a plurality of substrates in the form of a carbon heater by an induction heating heater. The susceptor has a mechanism for rotating itself and a mechanism for rotating the substrate. The sapphire substrate is placed in a spherical box that has been exchanged for nitrogen and placed on a carbon susceptor for heating 1. After the sample was introduced, nitrogen gas was passed through to purify the inside of the reactor. After circulating nitrogen gas for 8 minutes, the induction heating heater was operated, and after the substrate temperature was raised to 600 °C over 10 minutes, the pressure in the furnace was 15 kPa (150 mbar). While the substrate temperature was maintained at 600 ° C, hydrogen gas and nitrogen gas were allowed to flow while being left for 2 minutes to heat and clean the surface of the substrate. After the heating and cleaning is completed, the valve of the carrier gas of nitrogen is turned off ' -21 - 1304275 ' Only hydrogen is supplied to the reactor. • After the carrier gas is switched, the temperature of the substrate is raised to 1150 °C. After confirming that the temperature has stabilized at 1 150 °C, switch the valve of the piping of TMA1, and supply the gas containing the vapor of TMA1 to the reactor to cause decomposition with the deposit attached to the inner wall of the reactor. The atomic reaction begins the process of attaching A1N to the sapphire substrate. After 7 minutes and 30 seconds of treatment, the valve of the piping of TMA1 was switched, and the gas containing the vapor of TMA1 was stopped from being supplied to the reaction furnace. In this state, B stands by for 4 minutes, and waits until the TMA1 vapor remaining in the furnace is completely discharged. Next, the valve of the piping of the ammonia gas is switched, and the supply of ammonia gas into the furnace is started. After 4 minutes, the flow of the ammonia gas was continued while the substrate temperature was lowered to 1,040 ° C while the pressure in the furnace was 40 kPa (400 mbar). The flow rate of the flow regulator of the TMGa piping is adjusted during the temperature drop of the substrate. After confirming that the substrate temperature became 1040 ° C, the temperature was stabilized, and then the TMGa valve was switched to start supplying TMGa into the furnace to start the growth of undoped B GaN, and it took about 4 hours to grow the GaN layer. In this manner, an undoped GaN substrate layer having a film thickness of about 8 // m is formed. Further, a highly doped Ge n-type GaN contact layer is grown on the undoped GaN substrate layer. After the growth of the undoped GaN substrate layer, the TMGa was stopped from being supplied into the furnace, and thereafter the substrate temperature was raised to 1,080 ° C in one minute, and held for 3 minutes to stabilize the temperature. The throughput of TMGe is adjusted during this period. The amount of electrons that are circulated is adjusted to become a Ge-doped GaN contact layer with an electron concentration of about 2x1 (T9cirT3. The ammonia system is based on its original

SJ -22- • 1304275 ' The flow is continued to be supplied to the furnace. • After stabilization for 3 minutes, a film of GaN-doped η-type GaN with a thickness of 1 〇 nm and undoped GaN with a thickness of i〇nm is grown in a staggered manner for 100 cycles. 2 / zm n-type GaN contact layer. The Ge-doped n-type GaN layer is produced by supplying TMGa and trimethylsulfonium (TMGe) into a furnace, and the undoped GaN layer is produced by supplying TMGa. By this, an n-type G a N contact layer having an average carrier concentration of about 1 X 1 〇 19 c η Γ 3 is formed. After the final undoped GaN layer is grown, the TMGa valve is switched and the TMGa is stopped to supply the TMGa to the furnace. The ammonia gas flows while flowing in the original state, and the valve is switched on one side to switch the carrier gas from hydrogen to nitrogen. Thereafter, the substrate temperature was lowered from 1,080 °C to 720. (: The amount of SiH4 supplied is set while waiting for the temperature change in the furnace. The amount of the flow is adjusted in advance, and the electron concentration of the n-type InGaN coating layer adjusted to be doped with S i is lxl〇 18cnr3. The ammonia gas is continuously supplied to the furnace at its original flow rate. Thereafter, the state in the furnace is stabilized, and the valves of TMIii, TEGa B and SiH4 are switched, and the raw materials are supplied to the furnace. The In〇.〇2Ga〇.98N coating layer having a doping of Si having a film thickness of 20 nm was continuously supplied for a predetermined period of time. Thereafter, the valves of TMIn, TEGa, and SiH4 were switched to stop the supply of the raw materials. After the supply of the raw material is stopped, the setting of the supply amount of S i Η 4 is changed. The amount of the flow is adjusted in advance, and the electron concentration of the GaN barrier layer doped with Si is adjusted to 3 × 10 M c η Γ 3 . The formation of the G a N barrier layer doped with S i is performed as follows: At a substrate temperature of 720 ° C, TEGa and SiHN are initially supplied into the -23 - 1304275 furnace, and doped by a specified time. a layer of S a G a N consisting of a barrier layer A, then The supply of TEGa and SiH4 is stopped. Thereafter, the substrate temperature is raised to 920 ° C in the state of interruption and growth. After the temperature is stabilized, the pressure in the furnace, the flow rate and type of the ammonia gas and the carrier gas are in this state. Next, the valves of TEGa and SiH4 are switched, and the supply of TEGa and SiH4 to the furnace is started again, and in this state, the growth of the barrier layer B is performed at a substrate temperature of 920 ° C for a predetermined period of time. The temperature is lowered to 720 ° C, and in this state, the supply of TEGa and SiH 4 is continued. After the growth of the barrier layer C is performed, the valve is again switched to stop the supply of TEGa and SiH 4 to complete the GaN barrier layer. Therefore, a Si-doped GaN barrier layer having a total film thickness of 15 nm is formed in a barrier layer of a three-layer structure composed of A, B, and C. After the growth of the GaN barrier layer is completed, 30 seconds elapses. After stopping the supply of TEGa and SiH4, the substrate temperature, the pressure in the furnace, the flow rate and type of the ammonia gas and the carrier gas are switched, and the TEGa and SiH4 valves are switched, and TEGa and SiHU are supplied to the furnace. Form a well floor. Determined in advance B After the supply of TEGa and TMIn is performed in between, the valve is switched again, and only the supply of TMIn is stopped, and the growth of the In〇.〇8Ga〇.92N well layer is completed. At this point, an In〇 which becomes a film thickness of 3 nm is formed. .〇8Ga〇.92N Wells layer. Then, the supply of SiH4 is started again, and the formation of the barrier layer of the second layer is entered.

This step was repeated to form a 5-layer Si-doped GaN barrier layer and a 5-layer In〇.〇8Ga〇.92N well layer. In the manufacturing steps of the well layer and the barrier layer, after the barrier layer A is formed at 720 ° C, in the step of raising the temperature to 920 ° C for forming the barrier layer B -24 - 1304275, by stopping the ΠI The supply of the raw materials of the family interrupts the growth of the semiconductor. In the formation of the fifth layer of In. ·. 8G a. · After the 92N well layer, then proceed to the formation of the barrier layer of the sixth layer. In the formation of the barrier layer of the sixth layer, the supply of SiH4 is resumed, and after forming the barrier layer A composed of GaN doped with GaN, TEGa and SiH4 are continuously supplied to the furnace to raise the temperature of the substrate to 920. °C, and in this state, the growth of the barrier layer B is performed for a predetermined time at a substrate temperature of 920 °C. Next, the substrate temperature was lowered to 720. (:, > In this state, the supply of TEGa and SiH4 is continued, and after the growth of the barrier layer C is performed, the valve is again switched to stop the supply of TEGa and SiH4, thereby completing the growth of the GaN barrier layer. A Si-doped GaN barrier layer having a total film thickness of 15 nm is formed in a barrier layer of a three-layer structure composed of A, B, and C. By the above steps, a well layer having a thickness unevenness is formed (1st to 4th) a light-emitting layer of a multiple quantum well structure with a uniform thickness of the well layer (Layer 5). On the light-emitting layer of the Si-doped GaN barrier layer, a p-type Al〇.Q5Ga doped with Mg is formed. 〇.95N coating layer. After the supply of TEGa and SiH4 is stopped, and the growth of the Si-doped GaN barrier layer is completed, the substrate temperature is raised to 1 000 °C, and the type of carrier gas is switched to hydrogen and oxygen. The pressure in the furnace was changed to 15 kPa (150 mba.) After the pressure in the furnace was stabilized, the valves of TMGa, TMA1 and CP2Mg were switched, and the raw materials were started to be supplied into the furnace. Thereafter, after about 3 minutes passed, After growth, the supply of TEGa, TMA1 and CP2Mg is stopped to stop the doping of Mg-doped p-type Al 〇5Ga〇.95N coating growth. Thus, the shape -25304 is formed into a Mg-doped p-type Alo.^GamN coating layer having a film thickness of 16 nm. On the Ah.osGamN coating layer, a p-type Al〇.〇2Ga〇.98N contact layer is formed which is doped with Mg. The supply of TMGa, TMA1 and CPaMg is stopped, and Mg-doped Al〇.〇5Ga〇 is completed. After the growth of the .95N coating layer, the pressure in the furnace was changed to 20 kPa (200 mba.) After waiting for the pressure in the furnace to stabilize, the valves of TMGa, TMA1, and CP2Mg were switched, and the raw materials were started to be supplied into the furnace. The amount of CP2Mg circulating was previously reviewed, and the hole concentration of the p-type t Al〇.〇2Ga〇.98N contact layer doped with Mg was 8xl017cnT3. Thereafter, after about 12 minutes of growth, The supply of TMGa, TMA1, and CP2Mg is stopped to stop the growth of the Mg-doped p-type Al〇.〇2Ga〇.98N contact layer. Thereby, a Mg-doped P having a film thickness of about 0.2//m is formed. Type Al〇.〇2GaD.98N contact layer. After completing the growth of the Mg-doped p-type Al〇.〇2Ga〇.98N contact layer, the energization of the induction heating heater is stopped. The substrate temperature was lowered to room temperature for 20 minutes. In this cooling, only the ambient gas in the reaction furnace was made up of nitrogen gas, and then it was confirmed that the substrate temperature was lowered to room temperature, and the completed gallium nitride was formed. The compound semiconductor laminate is taken out to the atmosphere. By the above steps, a gallium nitride-based compound semiconductor laminate for a semiconductor light-emitting device is produced. Here, the p-type Alo.wGaowN contact layer doped with Mg exhibits a P-type even if an annealing treatment for activating the p-type carrier is not performed. Next, a gallium nitride-based compound semiconductor laminate is used to form a light-emitting diode which is one of semiconductor light-emitting elements. -26- 1304275

On the surface of the p-type AlGaN* contact layer of the formed gallium nitride-based compound semiconductor laminate, Pt, Rh, and Au are sequentially formed by laminating from the side of the contact layer by a method known in the art. Construct a reflective positive electrode. Thereafter, dry etching is performed on the gallium nitride-based compound semiconductor laminate to expose a negative electrode forming portion of the highly doped Ge n-type GaN contact layer, and Ti is sequentially deposited from the contact layer side in the exposed portion. A1 was made into a negative electrode. By these operations, an electrode having the shape shown in Fig. 2 was produced. The gallium nitride-based compound semiconductor having a positive electrode and a negative electrode as described above is laminated, and the back surface of the sapphire substrate is honed and honed to form a mirror-like surface. Thereafter, the gallium nitride-based compound semiconductor laminate was cut into individual wafers having a square shape of 305 μm, and was placed on the sub-fixing plate with the electrodes facing downward. The sub-fixing plate is placed on the lead frame, and the gold wire is connected to the lead frame to form a light-emitting diode. When a current is caused to flow in the forward direction between the positive electrode and the negative electrode of the light-emitting diode fabricated as described above, the forward voltage (driving voltage) at a current of 20 mA is 3.2V. Further, the emission wavelength was 460 nm, and the light emission output was 10.8 mW. I. The characteristics of such a light-emitting diode can be obtained without any deviation from the light-emitting diode which is made substantially from the entire gallium nitride-based compound semiconductor laminate. Further, before and after energization for 100 hours at a current of 30 mA, the voltage in the reverse direction of the current of 100 #Α was measured, and after the comparison, the rate of change in the reverse direction voltage was 〇%. Further, the third to tenth graphs are examples of photographs observed by one of the obtained wafers in a cross-sectional TEM and at a magnification of 1 〇〇〇. The observations were made for a 1304275 " section and were performed at 8 locations at 20 // m intervals. Well • The number of the floor is 1 to 5 from the surface side (semiconductor side) of the nitride semiconductor laminate structure. That is, the well layer 1 is located on the p-type layer side, and the well layer 5 is located on the n-type layer side. In the figure, A is a thick film portion, and B is a thin film portion. Further, in Figs. 3 to 10, the maximum film thickness and the minimum film thickness of each of the well layers in the portion are described. Table 1 shows that the eight locations shown in Figures 3 to 1 are combined to determine the maximum film thickness, minimum film thickness, average film thickness, and maximum film thickness and minimum film thickness of each well layer. The result of the ratio of the difference to the average film thickness. [Table 1] Maximum film thickness (nm) of the well layer Minimum film thickness (nm) Average film thickness (nm) Ratio of difference 1 3.1 2.8 2.95 ±5.1% 2 3.2 1.8 2.50 ±28.0% 3 3.1 1.9 2.50 ±24.0% 4 3.1 1.6 2.35 ±31.9% 5 3.2 1.7 2.45 ±30.6% It can be seen from Table 1 that the film thickness of the well layer 1 is within the average film thickness of ±5.1% and within 10%, so it is a well-layered well layer of the present invention. In addition, the film thickness range of the well φ layer 2 to 5 is an average film thickness of ±28.0%, ±24.0%, ±31.9%, and ±30.6%, and all of them exceed 1%, so the thickness of the present invention is uneven. Well household level. In the well layers 2 to 5, a portion thicker than the average film thickness of each is a thick film portion, and a film portion is a film portion. In the third to tenth figures, the barrier layer has a film thickness of about 15 nm. The barrier layer completely buryes the difference in film thickness between the film portion and the thick film portion of the well layer. In the eleventh to eighteenth drawings, the TEM photographs in the vicinity of the portions of the third to tenth graphs were observed by changing the magnification to 200,000 times. In all the figures, it is known that the well layer 1 is uniform in thickness. -28-.1304275 In these TEM photographs, the width of the thick film portion of the well layers 2 to 5 and the width of the film portion were measured, and the distribution thereof was evaluated. Further, the determination of the thick film portion and the film portion of each of the well layers is performed based on the average thickness of each of the above-mentioned well layers obtained from the third to the first drawings. Table 2 shows the results. For example, in the well layer 2 of the TEM photograph of Fig. 1, the thick film portion on the left side of the TEM photograph has a width of 250 nm, and then the film portion has a width of 60 nm, and then the thick film portion has a width of 1 0 5 . Nm, then 'the film portion is in the range of 35 nm', and the thick film portion is 75 nm, but in the table, a thick film portion (250 nm) - a thin film portion (60 nm) - a thick film portion (1 〇 5 nm) - a thin film portion ( 35 nm) - thick film portion (75 nm).

-29 - 1304275

[Table 2] TEM photograph of the distribution of the thick film portion and the thin film portion of the well layer _ Error film portion thick film portion 2 Thick film portion (250 nm) - Thin film portion (60 nm) Thick film portion (105 nm) - Thin film portion (35 nm) - Thick film portion (75nm) 35nm ~ 60nm 75nm ~ 250nm Increase 1 1 back 3 Thick film portion (260nm) - Thin film portion (45nm) Thick film portion (220nm) 45nm 220nm ~ 260nm Young 11 Figure 4 Thick film portion (160nm) - Thin film portion (100 nm) - Thick film portion (220 nm) 100 nm 160 nm to 220 nm 5 Thick film portion (260 nm V thin film portion (70 nm) · Thick film portion (12 〇 nm) 70 nm 120 nm to 260 nm 2 Thick film portion (41 〇 nm) - Thin film portion (35 nm) - Thick film portion (50 nm) - Thin film portion (3 Å nm) 30 nm to 35 nm 50 nm to 410 nm Fig. 12 Fig. 3 Thick film portion (470 nm) - Thin film portion G 〇 nm) 30 nm 470 nm 4 Film portion (185 nm) - thin film portion (4 〇 nm) - thick film portion (235 nm) - thin film portion (80 nm) 40 nm to 80 nm 185 nm to 235 nm 5 thick film portion (145 nm) - thin film portion dm) - thick film portion (245 nm) Thin film portion (40 nm) 40 nm to 50 nm 145 nm to 245 nm 2 thick film portion (270 nm) - thin film portion (65 nm) - thick film portion (20 nm) - thin film portion (55 nm) 55 nm to 65 nm 20 nm to 270 nm ^ φ: Λ ΟΓ ^ Ι 3 Thick film portion (320 nm) - Thin film portion (8 〇 nm) - Thick film portion (70 nm) is a film portion (50 nm) 50 nm ~ 80 nm 70 nm 〜 32 0 nm 弟13Fig. 4 Thick film portion (270 nm) - Thin film portion (9 Å nm) Thick film portion (120 nm > Thin film portion (30 nm) 30 nm to 90 nm 120 nm to 270 nm 5 Thick film portion (310 mn > Thin film portion (4 〇 nm) - Thick film portion (200 nm) 40 nm 200 nm to 310 nm 2 Thick film portion (190 nm) Thin film portion (60 nm) - Thick film portion (120 nm) Thin film portion (60 nm > Thick film portion (75 nm) 60 nm 75 nm to 190 nm αφ; 1 a rsi 3 Thick film portion (320 nm) Thin film portion (40 nm > Thick film portion (60 nm) - Thin film portion (60 nm) 40 nm to 60 nm 60 nm to 320 nm Younger 14 Fig. 4 Thin film portion (60 nm) - Thick film portion (65 nm) - Thin film portion ( 90 nm) - thick film portion (140 nm) - thin film portion (55 nm) 55 nm to 90 nm 65 nm to 140 nm 5 thick film portion (330 nm) thin film portion (45 nm) - thick film portion (65 nm) - thin film portion (60 nm) 45 nm to 60 nm 65 nm ~300nm 2 Thick film portion (450nm> Thin film portion (50nm) - Thick film portion (40nm) - Thin film portion (35nm) 35nm ~ 50nm 40nm ~ 450nm 1 c|SI 3 Thick film portion (580nm) - 580nm Brother 1!) Fig. 4 Thick film portion (520 nm) - Thin film portion (70 nm) 70 nm 520 nm 5 Thick film portion (540 nm) - Thin film portion (55 nm) 55 nm 540 nm 2 Thin film portion (40 nm) - Thick film portion (250 nm > Thin film portion (100 nm) - Thick film portion (130 nm) - thin film portion (60 nm) 40 nm to 100 nm 130 nm to 250 nm / φ: 1 Solid 3 Thick film portion (500 nm) Thin film portion (75 nm) 75 nm 500 nm Younger 16 Fig. 4 Thick film portion (580 nm) - 580 nm 5 Thick film portion (600 nm) - 600 nm 2 Thin film portion (65 nm) - Thick film portion (45 nm) - Thin film portion (30mn) - Thick film portion (320 nm) - Thin film portion (100 nm) 30 nm to 10 Å 0 nm 45 nm to 320 nm 1 otsi 3 Thick film portion (330 nm) - Thin film portion (50 nm) - Thick film portion (180 nm) 50 nm 180 nm to 330 nm 苐17Fig. 4 Thick film portion (60 nm) Thin film portion (100 nm) Thick film portion (300 nm) - Thin film portion (50 nm) 50 nm to 100 nm 60 nm to 300 nm 5 Thin film portion (40 nm) - Thick film portion (330 nm) - Thin film portion (60 nm) 40 nm to 60 nm 330 nm 2 Thin film portion (80 nm) - Thick film portion (95 nm) - Thin film portion (95 nm) - Thick film portion (140 nm) - Thin film portion (70 nm) 70 nm to 95 nm 95 nm to 140 nm 3 Thick film (130 nm), thin film portion (60 nm) - thick film portion (250 nm) - thin film portion (100 nm) 60 nm to 100 nm 130 nm to 250 nm, Fig. 18 Fig. 4 Thin film portion (70 nm) - thick film portion (275 nm) - thin film portion (90 nm) Thick film portion (100 nm) thin film portion (40 nm) 40 nm to 90 nm lOOnm to 275 nm 5 thin film portion (100 nm) - thick film portion (85 nm) - thin film portion (35 nm > thick film portion (105 nm) - thin film portion (6 〇) Nm) 35nm ~ lOOnm 85nm ~ 105nm From this table, when looking for the thin layer of each well When the width of the film portion and the thick film portion is distributed, the film portion is 30 to 10 nm for the well layer 2, 30 to 100 nm for the well layer 3, and 30 to 100 nm for the well layer 4, and the well layer 5 It is 35~100 nm. Further, the thick film portion is 20 to 450 nm for the well layer 2, 60 to 580 nm for the well layer 3, 60 to 580 nm for the well layer 4, and 65 to 600 nm for the well layer 5. -30- 1304275 (First comparative example) In the present comparative example, a gallium nitride-based compound semiconductor laminate was produced in the same manner as in the first embodiment except that all the well layers were formed into a well-thickness layer. That is, in the barrier layers of the first to fifth layers, the same as the sixth layer, 'after the formation of the barrier layer A, the TEGa and SiH4 are continuously supplied to the furnace, and the substrate temperature is raised to 9 2 0 °. Other than C, a gallium nitride-based compound semiconductor laminate was produced in the same manner as in the first embodiment. Using this gallium nitride-based compound semiconductor laminate, a light-emitting diode was produced in the same manner as in the first example and evaluated. As a result, the forward voltage of the current of 20 mA was 3.9V. In addition, the emission wavelength is 460 nm, and the light-emitting output shows 9 m W. In addition, the initial voltage of the reverse voltage of 10 μA is compared with the reverse voltage of 10//A after the current of 30 mA for 30 hours. The rate of change in the reverse direction voltage is -0.5%. (Second Comparative Example) In the present comparative example, a gallium nitride-based compound semiconductor laminate was produced in the same manner as in the first embodiment except that all the well layers were formed as a well layer having a non-uniform thickness. In other words, in the barrier layer of the sixth layer, similarly to the first to fifth layers, after the barrier layer A is formed, the TEGa and SiH4 are stopped and supplied to the furnace, and the substrate temperature is raised to 920 ° C. A gallium nitride-based compound semiconductor laminate was produced in the same manner as in the first embodiment. Using this gallium nitride-based compound semiconductor laminate, the light-emitting diode was produced in the same manner as in the first example and evaluated. As a result, the forward voltage of the current of 20 mA was 3.15 V. In addition, the emission wavelength is 460nm ’

SJ -31 - 1304275 shows 9mW 〇In addition, the initial 値 of the reverse direction voltage of 1 〇# A and the reverse direction voltage 10 of 10//A after 100 hours of current supply of 30 mA, the rate of change of the reverse direction voltage It is -7 %. (Second Embodiment) In the present embodiment, a gallium nitride-based compound semiconductor laminate was produced in the same manner as in the first embodiment except that only the well layer closest to the n-type layer was formed into a uniform layer having a uniform thickness. . In other words, in the barrier layer of the second layer, in the same manner as the sixth layer of the first embodiment, after the barrier layer is formed, TEGa and SiH4 are continuously supplied to the furnace, and the substrate temperature is raised to 920 °C. And in the barrier layer of the sixth layer, in the same manner as the first to fifth layers of the first embodiment, after the barrier layer A is formed, the supply of TEGa and SiH4 to the furnace is stopped, and the temperature of the substrate is raised to 920 °C. A gallium nitride-based compound semiconductor laminate was produced in the same manner as in the first embodiment. Using this gallium nitride-based compound semiconductor laminate, a light-emitting diode was produced in the same manner as in the first example and evaluated. As a result, the current of 20 mA in the forward direction was 3.3 V, the emission wavelength was 460 nm, and the light-emitting output showed 10.8 mW. (Third Embodiment) In the present embodiment, the gallium nitride system is formed in the same manner as in the first embodiment except that the well layer of the third layer is formed from the p-type layer as the well layer having the uniform thickness. Compound semiconductor laminate. In other words, in the barrier layer of the fourth layer, in the same manner as the sixth layer of the first embodiment, after the barrier layer A is formed, TEGa and SiH4 are continuously supplied into the furnace, and the substrate temperature is raised to 8, 32- 1304275 9 20 ° C, and in the barrier layer of the sixth layer, in the same manner as the first to fifth layers of the first embodiment, after forming the barrier layer A, the supply of TEGa and SiH4 to the furnace is stopped, and A gallium nitride-based compound semiconductor laminate was produced in the same manner as in the first embodiment except that the substrate temperature was raised to 920 °C. Using this gallium nitride-based compound semiconductor laminate, a light-emitting diode was produced in the same manner as in the first example and evaluated. As a result, the current of 20 mA in the forward direction was 3.2 V, the emission wavelength was 46 Onm, and the luminous output showed 9.7 mW. (Fourth Embodiment) > In the present embodiment, except that only the well layer closest to the P-type layer and the well layer closest to the n-type layer are made into a well-layer having a uniform thickness, the other and the first In the same manner as in the examples, a gallium nitride-based compound semiconductor laminate was produced. In other words, in the barrier layer of the second layer, the same as the sixth layer, after the barrier layer A is formed, TEGa and SiH4 are continuously supplied to the furnace, and the substrate temperature is raised to 920 ° C. A gallium nitride-based compound semiconductor laminate was produced in the same manner as in the first embodiment. Using this gallium nitride-based compound semiconductor laminate, a light-emitting diode was produced in the same manner as in the first example and evaluated. As a result, the current of 20 mA in the forward direction was 3.45 V, the emission wavelength was 460 nm, and the luminous output showed 1 1.4 mW. (Fifth Embodiment) In the present embodiment, the two well layers of the first and second layers are formed into a well-layer having a uniform thickness from the number of P-type layers, and the other embodiments are the same as in the first embodiment. A gallium nitride-based compound semiconductor laminate. That is, in the barrier layer of the fifth layer, as in the sixth layer, after the barrier layer A is formed, the state of -33 - 1304275 TEGa and SiH4 is continuously supplied to the furnace, and the substrate temperature is raised to 920 t. A gallium nitride-based compound semiconductor laminate was produced in the same manner as in the first embodiment. Using this gallium nitride-based compound semiconductor laminate, a light-emitting diode was produced in the same manner as in the first example and evaluated. As a result, the forward voltage of the current of 20 mA was 3.2 V, the emission wavelength was 460 nm, and the light-emitting output showed 10.2 mW. (Sixth embodiment) In the present embodiment, the same applies to the first embodiment except that the three well layers of the first to third layers are formed from the p-type layer to form a well layer having a uniform thickness. A gallium nitride-based compound semiconductor laminate. That is, in the barrier layers of the fourth and fifth layers, as in the sixth layer, after the barrier layer A is formed, TEGa and SiH4 are continuously supplied to the furnace, and the substrate temperature is raised to 9 20 °C. A gallium nitride-based compound semiconductor laminate was produced in the same manner as in the first embodiment. Using this gallium nitride-based compound semiconductor laminate, a light-emitting diode was produced in the same manner as in the first example and evaluated. As a result, the forward voltage of the current of 20 mA was 3.35 V, the emission wavelength was 460 nm, and the light-emitting output showed 1 0 · 2 mW. (Seventh embodiment) In the present embodiment, the positive electrode and the negative electrode are provided in the gallium nitride-based compound semiconductor laminate according to the first embodiment, but the structure of the positive electrode is p. - The transparent electrode of Au and Ni 依 is sequentially laminated on the surface of the AlGaN contact layer, and the structure of the pad of the Ti, Au, Α, and Au is sequentially laminated thereon, and the structure of the S) -34 - .1304275 electrode is formed. As in the first embodiment, as a result of evaluating the performance of the light-emitting diode, the forward voltage of the current of 20 mA was 3.2 V, the emission wavelength was 460 nm, and the light-emitting output showed 5.5 mW. The characteristics of such a light-emitting diode can be obtained without error for the light-emitting diode which is formed substantially from the total thickness of the formed gallium nitride-based compound semiconductor laminate. (Third Comparative Example) In the comparative example, a gallium nitride-based compound semiconductor laminate produced by the first comparative example was used, and a light-emitting diode having an electrode structure was produced in the same manner as in the seventh embodiment. As a result of evaluating the performance as in the first embodiment, the forward voltage of the current of 20 mA was 3.9 V, the emission wavelength was 460 nm, and the light-emitting output showed 5 mW. (Fourth Comparative Example) In the comparative example, a gallium nitride-based compound semiconductor laminate produced by the second comparative example was used, and a light-emitting diode having an electrode structure was produced in the same manner as in the seventh embodiment. As a result of evaluating the performance as in the first embodiment, the forward voltage of the current of 20 mA was 3.15 V, and the emission wavelength was 460 nm. The luminous output showed 5 mW. (Industrial Applicability) The light-emitting element obtained by using the gallium nitride-based compound semiconductor laminate of the present invention has a low driving voltage and a high light-emitting output, so that the industrial use price is extremely large. -35- 1304275 [Brief Description of the Drawings] * Fig. 1 is a schematic view showing a cross section of a gallium nitride-based compound semiconductor laminate produced by the examples and the comparative examples. Fig. 2 is a schematic view showing the electrode structure of the light-emitting diodes produced in the examples and the comparative examples. Fig. 3 is a view showing an example of a cross-sectional TEM photograph of a gallium nitride-based compound semiconductive volume layer produced in the first embodiment. Fig. 4 is a view showing another example of a cross-sectional TEM photograph of the gallium nitride-based compound semiconductive ® volume layer produced in the first embodiment. Fig. 5 is a view showing still another example of a cross-sectional TEM photograph of the gallium nitride-based compound semiconductive volume layer produced in the first embodiment. Fig. 6 is a view showing still another example of a cross-sectional TEM photograph of the gallium nitride-based compound semiconductive volume layer produced in the first embodiment. Fig. 7 is a view showing still another example of a cross-sectional TEM photograph of the gallium nitride-based compound semiconductive volume layer produced in the first embodiment. Fig. 8 is a view showing still another example of a cross-sectional TEM photograph of the gallium nitride-based compound semi-conductive I volume layer produced in the first embodiment. Fig. 9 is a view showing still another example of a cross-sectional TEM photograph of the gallium nitride-based compound semiconductive volume layer produced in the first embodiment. Fig. 10 is a view showing still another example of a cross-sectional TEM photograph of the gallium nitride-based compound semiconductive volume layer produced in the first embodiment. Fig. 1 is a view showing still another example of a cross-sectional TEM photograph of the gallium nitride-based compound semiconductive volume layer produced in the first embodiment. Fig. 1 is a view showing still another example of a cross-sectional TEM photograph of a gallium nitride-based compound semiconductor-36 - 1304275 - volume layer produced by the first embodiment. • Fig. 1 is a view showing still another example of a cross-sectional ΤΕΜ photograph of the gallium nitride-based compound semi-conductive volume layer produced in the first embodiment. Fig. 14 is a view showing still another example of a cross-sectional ΤΕΜ photograph of the gallium nitride-based compound semi-conductive volume layer produced in the first embodiment. Fig. 15 is a view showing still another example of a cross-sectional ΤΕΜ photograph of the gallium nitride-based compound semi-conductive volume layer produced in the first embodiment. Fig. 16 is a view showing still another example of a cross-sectional ΤΕΜ photograph of the gallium nitride-based compound semi-conductive t-volume layer produced in the first embodiment. Fig. 17 is a view showing still another example of a cross-sectional ΤΕΜ photograph of the gallium nitride-based compound semi-conductive volume layer produced in the first embodiment. Fig. 18 is a view showing still another example of a cross-sectional ΤΕΜ photograph of the gallium nitride-based compound semi-conductive volume layer produced in the first embodiment.

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Claims (1)

1304275 • X. Patent application scope: ' 1. A gallium nitride-based compound semiconductor laminate having a η-type layer, a light-emitting layer and a Ρ-type layer on a substrate, the light-emitting layer being interlaced by the well layer and the barrier layer a multiple quantum structure of the laminate, and the light-emitting layer is configured to be held by the n-type layer and the Ρ-type layer, and is characterized in that: the well layer constituting the multiple quantum structure is formed by a well layer having a uniform thickness and a uniform thickness It is composed of the wells. 2. The gallium nitride-based compound semiconductor laminate according to the first aspect of the patent application, wherein the well layer closest to the p-type layer has a uniform thickness. 3. A gallium nitride-based compound semiconductor laminate according to claim 1, wherein the well layer closest to the n-type layer has a uniform thickness. 4. The gallium nitride-based compound semiconductor laminate according to claim 1, wherein the film thickness of the well layer having a uniform thickness is 1.8 to 5 nm. 5. The gallium nitride-based compound semiconductor laminate according to claim 1, wherein the film portion of the well layer having a non-uniform thickness is 2.7 nm or less. 6. The gallium nitride-based compound semiconductor laminate according to claim 1, wherein the multiple quantum well structure has a structure in which the well layer and the barrier layer are laminated 3 to 10 times. 7. The gallium nitride-based compound semiconductor laminate according to claim 1, wherein the barrier layer is a gallium nitride selected from the group consisting of InGaN having a ratio of In which forms GaN, AlGaN, and InGaN of the well layer. A compound semiconductor. 8. For example, the gallium nitride-based compound semiconductor laminate of the seventh aspect of the patent application is -38- 1304275, wherein the barrier layer is GaN. 9. A gallium nitride-based compound semiconductor laminate according to claim 1, wherein the barrier layer dopant is a dopant. i 〇. A gallium nitride-based compound semiconductor laminate according to claim 9 wherein the dopant is from C, Si, Ge, Sn ' Pb, 〇, S, Se, Te, Po, Be, Mg, At least one selected from the group consisting of Ca, Sr, Ba, and Ra. 1 1. A gallium nitride-based compound semiconductor laminate according to claim 9 wherein the concentration of the dopant is lxl 〇 17 cm·3 to lxl 018 cm·3. > 1 2 The gallium nitride-based compound semiconductor laminate according to the first aspect of the invention, wherein the barrier layer has a film thickness of 7 to 50 nm. The gallium nitride-based compound semiconductor laminate according to Item 12 of the patent application, wherein the barrier layer has a film thickness of 14 nm or more. 1 4 . The gallium nitride-based compound semiconductor laminate according to claim 1, wherein the well layer contains In. A gallium nitride-based compound semiconductor laminate as described in claim 14 wherein a thin layer containing no In is present on at least the substrate side surface of the barrier layer. a gallium nitride-based compound semiconductor light-emitting device characterized in that a negative electrode is provided in an n-type layer of a gallium nitride-based compound semiconductor laminate according to any one of claims 1 to 15 The profile layer is set to the positive electrode. 1 7 - A type of lamp 'Using a gallium nitride-based compound semiconductor light-emitting element of claim 16 of the patent application. 1 8 · The scope of application for patents is 1st! The method for producing a gallium nitride-based compound semiconductor laminate according to any one of the five items, characterized in that: after forming the well layer -39 - 1304275, 'by forming the thickness of the portion of the well layer by decomposition or sublimation Uneven wells. 1 . The method for producing a gallium nitride-based compound semiconductor laminate according to claim 18, wherein a substrate temperature T1 when forming a well layer and a substrate temperature T2 when the portion of the well layer is decomposed or sublimated , for T1 S T2. A method for producing a gallium nitride-based compound semiconductor laminate according to claim 18, wherein the decomposition or sublimation of the portion of the well layer is carried out by a gas containing a nitrogen source and not containing a source of a group III metal Under the environment. 2 1 The method for producing a gallium nitride-based compound semiconductor laminate according to claim 18, wherein the decomposition or sublimation of the portion of the well layer is carried out in the step of forming the barrier layer. 'public -40-