TW451505B - Epitaxial wafer for luminous semiconductor element and luminous semiconductor element - Google Patents

Abstract

The present invention is to provide an epitaxial wafer for luminous semiconductor element using n-type GaP single crystal substrate which has high brightness and less dispersion in brightness. It is achieved by most appropriately defining the density of boron in the n-type GaP single crystal substrate.

Description

4 5 15 0 5 A7 B7 V. Description of the invention (丨) [Technical field to which the invention belongs] The present invention includes a GaP bar, GaAsP 糸, and an AlGalnP 糸 epitaxial wafer for light-emitting semiconductor devices and light-emitting semiconductor devices, especially related to providing A high-brightness, light-emitting semiconductor element epitaxial wafer with little unevenness, and a light-emitting semiconductor element made from the epitaxial wafer. [Conventional Technology] The visible light emitting diode is widely used in various display devices and the like because of its low power consumption K and long life. In particular, due to the recent improvements in technology, high brightness, and the variety of luminous colors introduced by the introduction of new crystalline materials, the use and use of them have increased. Among these light-emitting diodes, GaP single crystal substrates are used. As substrates, there are light-emitting diodes of GaP, GaAsP, and AlGalnPG. As GaP 糸 light-emitting diodes, three types of light-emitting diodes, such as red, yellow, and pure green, are fabricated by the liquid-phase epitaxial growth method. Since GaP migrates indirectly, red and yellow-green light-emitting diodes are introduced with a light-emitting center to achieve high brightness. The red light-emitting diode is a structure in which an η-type GaP epitaxial layer and a ρ-type GaP epitaxial layer of zinc (Zπ) and dope oxygen are formed on an η-type GaP single crystal substrate. The Zn- A pair of 0 is the emission center, and the emission wavelength will emit red light of about 70η B. A yellow linear light-emitting diode is formed on an n-type GaP single crystal substrate. After forming an n-type GaP buffer layer as necessary, an n-type GaP epitaxial layer is formed, and the n-type GaP epitaxial layer is doped with ytterbium (N) as a light emitting center. Layer and p-type GaP-type epitaxial layer, the emission wavelength will emit yellow-green light of about 570nffl. This paper size applies to China National Standard (CNS) Α4 specification (210X297 mm) I ------- 1¾ clothing ------, 1T ----- line (Please read the precautions on the back before (Fill in this page) Printed by the Consumer Cooperative of the Central Government Bureau of the Ministry of Economic Affairs 15 0 5 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (2) Pure green light-emitting diodes are monocrystalline Γ1 GaP After forming an n-type GaP buffer layer on the substrate as necessary, an n-type GaP epitaxial layer and a p-type GaP epitaxial layer doped with nitrogen (N) are formed. Since the light-emitting center is not used, it emits light with the yellow-green light described above. Although the brightness of the diode is lower than that of the diode, a pure green light emission with a wavelength of 555πβ can be obtained.

Ga As P series light-emitting diode system K vapor phase epitaxial growth method. Because the lattice constants of GaP and GaAsP are different, so on a η-type GaP single crystal substrate, first, a vapor phase epitaxial growth method is used to form a η-type Ga AsP composition gradient layer, and then a vapor phase epitaxial growth method is also used to form an η-type. G a A s P composes a certain layer, where n-type G a A s P composes the surface of a certain layer _ diffusion Z η to form a ρ η bond. By changing the composition of As and P in a certain layer of η-type GaAsP, the luminous color of red (660nn) through orange (610nra) to yellow (59〇Γί «ι) can be obtained. In addition, if the composition of P is high, it will become indirect migration, so NM will be doped as luminescent center to achieve high brightness.

AlGalnP-based light-emitting diode system is produced by the main M organic Au chemical vapor growth method (MOCVD method). Although GaAs single crystal substrates are often used, they can also be produced using GaP single crystal substrates. The band gap of GaAs is smaller than the band gap of AlGalnP in the active layer, so K absorbs light *, but GaP is larger than the band gap of AlGalnP, so M does not absorb light. Therefore, if GaP is used as a substrate, the light emitted from the active layer to the * side of the substrate cannot be absorbed, and it will have high brightness. When GaP is used as a substrate, the GaP and AlGalnP grid-4 -This paper size is applicable to China National Building Vehicle (CNS) A4 specification (210'X 297 mm) I i ------ IT ------ 0 (Please read the precautions on the back before filling this page ) 4 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5 15 0 5 A7 __B7_ V. Description of the Invention (4) The constants are different, so on the η-type GaP single crystal substrate, first, the MOCVD method is used to form Ir »GaP After the gradient layer composed of AlGaltiP or AllnP, a η-type A 1 G a I η P cladding layer (c 1 ad layer), an AlGalnP active layer, and a P-type AlGalnP cladding layer are formed by the M MW 0 CVD method. If necessary, a contact layer or a window layer is formed on it. The coating can also be made into AllnP. As the crystallization of the contact layer or the window layer, GaAs, GaAlAs, GaP, etc. are usually used as the growth method of these layers. In addition to MOCVD, other growth methods such as epitaxial epitaxial growth can also be used.

AlGaltiP-based light-emitting diodes can change the crystalline composition of the AlGalnP active layer to obtain green light from 640nn red through orange, yellow to 550 nm green. The above-mentioned GaP-based, GaAsP-based, and AlGalnP 糸 light-emitting diode systems are all made of ti-type GaP single-crystal substrates using Te, Si, etc. as dopants. [Problems to be Solved by the Invention] Although the brightness of some light-emitting diodes has been improved due to recent technological improvements, the market demand is for higher brightness. In addition, with the expansion of applications such as large displays, the demand for reducing uneven brightness is increasing. An object of the present invention is to provide a light-emitting semiconductor element such as an epitaxial crystal for a light-emitting diode with high brightness and little unevenness, and a light-emitting diode produced from the epitaxial wafer. [Means of Solving Problems] This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) —. ------ ΪΤ ----- ^ (Please read the notes on the back before filling (This page) 451505 A7 B7 V. Description of the invention (+) The epitaxial wafer for a light-emitting semiconductor device of the present invention is formed on an n-type GaP single crystal substrate, and at least an n-type semiconductor epitaxial epitaxial layer and a p-type semiconductor epitaxial layer are formed. The epitaxial crystal for a light-emitting semiconductor device is made of boron (B &gt;) of the n-type GaP single crystal substrate with a lx 1ϋ ^ cir3 or less, preferably 5X10 i6chT3 or less, so as to reduce uneven brightness. The upper η-type semiconductor semiconducting epitaxial layer and the p-type semiconductor epitaxial layer can be most suitably applied to epitaxial crystals for light-emitting semiconductor devices. In addition, the upper η-type semiconductor epitaxial layer and the above-mentioned p-type semiconductor epitaxial layer are: Applicable to epitaxial wafers for light-emitting semiconductor devices made of GaAsx PniiKxCl). The n-type semiconductor epitaxial layer and the p-type semiconductor epitaxial layer of the present invention are applicable to epitaxial crystals for light-emitting semiconductor plaque elements composed of (Alx Ganiy. Im-YPftXxU, 〇 &lt; y &lt; l &gt;). In addition, the present invention is a light-emitting semiconductor element made of the above-mentioned epitaxial wafer for a light-emitting semiconductor element. The morphologically-implemented Mingfa crystal epitaxial external body has a uniform color ω I degree P, and the lower the bright Ga, and For the first time, Liang and other experts have clearly discussed the issue of the test copy, Μ I --------- install ------ order ----- line (please read the precautions on the back before filling in this Page) The degree of printing η printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Ga concentrated body η is loaded into the homogeneous phase process and mixed with the same substance to blend the homogeneous phase, and the plate-based crystal 6a is used to form Single PP, a and S layers extend LT. Even if it is bright, the body of the master will be uniform. The seed that is not even bright will be obtained. This is obtained by making the same crystal and extending it. The layer is extended and extended, so the crystallized single P of 93 is produced in the next batch. Ηα G type η ο The paper size applies to the Chinese National Standard {CNS) A4 (210 × 297 mm) printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 _ B7 V. Description of the invention (F) Then, after a detailed review of the various physical properties and brightness of the η-type GaP single crystal substrate, it is understood that there is a real phase between the boron (B) saturation and brightness in the η-type GaP crystal substrate.鼷 兰 傜. In other words, the epitaxial crystal H was formed by forming the η-type GaP epitaxial layer and the P-type GaP epitaxial layer on the same type of η-type GaP single crystal substrate with different B concentrations by using the same process, and investigated the brightness and In the case of artifacts with a B concentration in a η-type SaP single crystal substrate, the B-brightness is IX 10 17 ci · 3 or less, preferably 5 × 10 ibcb · 3 or less. The high-brightness and minimal unevenness epitaxy are broadcast. Epistar »So, using η-type GaP single crystal substrates as the substrate, GaP yellow color, GaP pure green, GaAsP strips and epitaxial wafers for AlGalnP 糸 light-emitting diodes were investigated similarly. The concentration of B in crystal substrates depends on the brightness. As a result, it was found that the epitaxial crystals for any of the above-mentioned light emitting diodes are also used, and it is preferable that the B gradient in the η-type GaP single crystal substrate is lx i0i7Cm · 3, preferably 5x10 mm. (: · -3 or less, an epitaxial wafer with high brightness and less uneven brightness can be obtained. In addition, the degree of B in a η-type GaP single crystal substrate is measured by secondary ion mass analysis (SIHS). η-type GaP single crystal substrates are usually obtained from π-type GaP single crystals produced by the liquid-tight Czochralski nethod (LEC) method. In the 1 ^ (: method, B2O3 is used. As a sealant, it is easy to incorporate B into the crystal, and it is easy to become a concentration of more than 10. Therefore, the conditions for the formation of single crystals must be appropriately selected to reduce the amount of B incorporated into the crystal. -7-This paper size is applicable to China National Standard (CNS) A4 Specification (2 丨 0X297mm) I n tl--I i I lmnnnn T n I n I (Please read the precautions on the back before filling this page) Staff Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs Printing 4 5 1 5 0 5 A7 B7 V. Description of invention (P) as a way to reduce B For example, see the method of adjusting the concentration of moisture contained in team 0 to suppress the decomposition of B2 03. Also, by adding a small amount of gaseous compounds such as P2 0 or Ga2 03 to 10 »can also be reduced ^ In addition For example, B can be reduced by adjusting the holding time or pulling speed before the start of single crystal pulling up. ^ There seem to be several other ways to reduce B. Considering other characteristics of single crystals, choose from these methods. Or combined and applicable, the degree of B in the crystal can be controlled to 1 X 1 0 «c I · 3 or less, and more preferably 5 X 10 or less ca_3. [Example 1 The details of the present invention are based on the examples. The description is as follows. <Example 1> First, an example of a GaP red diode will be described. The outline of the epitaxial crystal structure for GaP red light emitting diodes produced in this example is shown in FIG. In Fig. 1, a pseudo-n-type GaP single crystal substrate, two like an n-type GaP epitaxial layer, and a p-type GaP epitaxial layer doped with Zn and 0. As the n-type GaP single-crystal substrate 1, a liquid-tight seal chip is used. The Te-doped GaP single crystal substrate produced by the Leusch (LEC) method has a carrier concentration of 2 &gt; &lt; 1017 (; 8 * 3, the main surface is (111) 8 planes.) In the known substrate of the horizontal slide plate, the n-type SaP single crystal substrate 1 on the upper side is set, and the solution is set as a growth solution. The amount of Ga metal and GaP crystal, and silicon as a dopant are specified. Still in the state of separating the substrate and the growth solution, the slide plate is set to epitaxial growth, and the temperature is increased to IGOO-C under a hydrogen flow. Hold for 1 hour. For the national standard of Ga metal solution paper, use the Chinese National Standard {CNS) A4 specification (210X297 mm), I order (please read the precautions on the back before filling this page) A7 j 15 0 5 B7 V. Description of the Invention (7) Polycrystallines which are decomposed to saturated GaP. Thereafter, the substrate holder was slid to contact the substrate 1 and the growth solution, and the substrate holder 1 was slowly cooled to 80 ° C to form an n-type GaP epitaxial layer 2 doped with silicon on the substrate 1. After the growth is completed, the substrate 1 of the growing η-type GaP epitaxial layer 2 and the growth solution are separated by sliding the substrate holder, and after cooling to room temperature, the substrate 1 of the growing η-type GaP epitaxial drawer 2 is taken out. Then, on the substrate holder of the slide board, the substrate 1 for growing such an n-type GaP epitaxial layer 2 is set, and the requirements for Ga metal, GaP polycrystal, Zn, and Ga2 03 for the growth solution are set in the solution pond. the amount. This slide was set to epitaxial growth, heated to 10QO-C under a stream of hydrogen, and kept for 1 hour for Ga metal until the planer and GaP polycrystals were dissolved. After that, the substrate holder was slid to contact the substrate 1 and the solution for growth of the n-type GaP epitaxial layer 2 and the temperature was raised to 105 ° C to dissolve a part of the surface of the n-type SaP epitaxial layer 2. Slowly cooled to 950 ^ 0, and on the n-type GaP epitaxial layer 2, a p-type GaP epitaxial layer 3 doped with Zn and 0 was grown. After the growth was completed, the substrate 1 and the growth solution were separated from the growth n-type GaP epitaxial layer 2 and P-type GaP epitaxial layer 3 by sliding the substrate holder, and cooled to room temperature to obtain a GaP red light-emitting epitaxial epitaxy. Wafer ^ In this Example 1, by reducing the amount of water in 03 used in the growth of a GaP single crystal to reduce the B concentration in the crystal, a B concentration phase in the crystal was made IX 10 17 cur3 or less and a B concentration phase was produced. Three different levels of η-type P single crystal substrates. An epitaxial wafer for a GaP red light-emitting diode was fabricated using the n-type GaP single crystal substrate in the above process. Thereafter, the paper size of the obtained 6aP red light-emitting diode epitaxial wafers is subject to the Chinese National Standard (CNS) Λ4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page) Ministry of Economic Affairs The Central Standards Bureau's Consumer Cooperative Cooperative Printing 15 0 5 A7 B7 V. Description of the Invention (ί) Product 0 Different surface types P and surface types η and H * The processing has been added to control components 0 and then P ' The pole 1 η is formed by the etched photoreceptor, the second light emission and the degree of a G, Pan, and the obtained B. The base is c. The third example is shown in Figure 3, which shows that the body is brighter than the medium crystal, while the single crystal growing technique is known as "3." "1" is prepared, and the contrast is B.

X 17 type η has a high degree of heterogeneity B and the upper type is installed. (---- Please read the precautions on the back before filling this page). The poles 1-3 two light and its 3 colors are used ^ a child P a 〇6 quasi-water seeding process 3 slabs on the basis of crystals to form a single crystal, 〇-type plate example Ga applied and obtained, Later, it will be the same type of the same type of the c η body of the second crystal light extension P 3 a with r J body. The second light color is red. At the time shown in the table, the result of the same plate fruit-based crystal 1 single example The degree of the implementation of the system of the degree of bright body pole two light emission concentration Figure -11 2 by

If you know X 17, you can get 3 pictures. · Η Crystal Form P B G Type η is good at X 5 is the most economical Ministry of the Central Building Standard Bureau staff consumer cooperatives printed a form PB G. The degree C of the light and the height are not true, and the body is bright, and the light retransmission X is 17 as 1-η &lt; τ C. ί- i [板 1-3 基 体 ηρίΕΕ CB ™ 掻 之 ap The crystal r-tfGa is the result of the concentration of the strong Β. The technique of the light of the high concentration of the medium 掻 is used to learn the color and red, ap to G is 01. ί —Λ ςρ For the extension of the monolayer ρ xi a, the 6 type body 115 is used as the degree, and the thick film B crystal is used for the extension of the middle and outer plates σ

X 1? For the sake of your majesty, you will use c to settle the borrowing order. P 2 3 3 The color of the paper is η. The paper scale is applicable to the Chinese National Standard (CNS) Ad specifications (210X 297 mm) 451505 A7 B7 Central Ministry of Economic Affairs Printed by the Standards Bureau Consumers Cooperative Co., Ltd. 5. Description of the Invention (9) The β 潺 degree in the crystal substrate is made to be less than ixi〇17c · * 3, which can make the GaP red light-emitting epitaxial wafers have uneven brightness. The hook is smaller. &lt; Embodiment 2 &gt; An example of a GaP yellow edge light emitting dipsum will be described below. The structure of the epitaxial crystal K of GaP yellow edge light-emitting diode fabricated in this example is shown in the third country. In Figure 3, 4 pseudo-n-type GaP single crystal substrates, 5 like n-type GaP entanglement, 6 僳 Si doped n-type GaP epitaxial layer, 7 僬 doped cyanide (H) n-type GaP epitaxial layer, 8 for P-type GaP epitaxial layer. As the η-type Gap single crystal substrate 4, a Te-doped GaP single crystal substrate produced by the liquid-sealed Cheklaussky UEC) method was used, and the pandepande was set to 2 乂 1017 (; 1 |- 3, the main surface is set to (111) 8 surface. First, on this single crystal plate 4, the box is formed by a conventional liquid phase epitaxial growth method to fear the n-type GaP retardation layer 5. This n-type GaP buffer layer It is Si-doped, with a loading concentration of 4X10 I? Cb-3 and a layer thickness of 100 //. The substrate holder of the well-known tracing slide is set to grow the n-type 6aP buffer layer 5 of the n-type. The GaP single crystal substrate 4 is set in the solution tank as a predetermined amount of Ga gold tincture. Still in the state of separating the substrate and the metal, this slide plate is mounted on the epitaxial growth tincture, and heated to At 1000Ό, slide the substrate holder to contact the surface of the η-type GaP strand layer 5 with Ga metal, and hold it for 1 hour for the Ga metal to dissolve into a part of the saturated η-type GaP buffer layer 5. At this time, the π-type GaP buffer is dissolved A part of layer 5 is used as the quartz of the reaction tube of the Si epitaxial growth furnace contained in the dopant, and the Si produced by the reduction of tritium hydrogen is dissolved in Ga gold. 1-This paper size applies to national standards (CNS M4 specifications (210X297 mm) [........ FI __ .1 f III 丁 ni II n -1 II (Please read the precautions on the back before (Fill in this page) Imprint 1 of the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 1 δ 1 5 Ο 5 Α7 Β7 V. Description of the Invention (^) Afterwards, it was slowly cooled to 960 ° C and Si doped on the η-type GaPii layer 5 The hetero π-type GaP epitaxial layer 6 β is connected, and the temperature is maintained at 96E) ° C, and the atmosphere gas is switched from hydrogen to argon gas with a predetermined amount of ammonia gas added. &Lt; The gas solution reacts with each other and takes ytterbium (N) into the Ga solution. Thereafter, it is cooled to 90 ° C. and H-doped η-type GaP epitaxy is grown on the Si-doped η-type GaP epitaxial layer 6. Layer 7. The male inlay still keeps the temperature at 9G0 ° C. Supply zinc (Zn) vapor in the atmosphere and take a specified amount of zinc β in the Ga solution. Then cool the temperature to 800 ° C and dope in N. On the n-type GaP epitaxial layer 7, a Ztl-doped P-type GaP epitaxial layer 8 was grown. After the growth was completed, the substrate holder was slid to separate the growth solution, and the solution was cooled to room temperature to obtain Epitaxial wafers for GaP yellow edge light emitting diodes. In this Example 2, the concentration of B in crystals was reduced by reducing the water content in B2 03 used for the growth of GaP single crystals to produce B in crystals. Three levels β of η-type GaP single crystal substrates with different concentrations of B below IX 10 π cm · 3 but different B concentrations. Using the η-type GaP single-crystal substrate, the above process was used to produce a GaP yellow edge light-emitting diode. Epitaxial crystals. Thereafter, AuGe and AuBe were deposited on the η-type surface and the P-type surface of the obtained GaP yellow-green light-emitting diode epitaxial wafer, respectively, heat treatment was applied, and photo-etching was used to form an η electrode and a p-electrode. After separation, a GaP light-emitting dimer was produced. Fig. 4 shows the relationship between the 8 concentration in the n-type S a P single crystal substrate of the epitaxial crystalline GaP yellow-green light-emitting diode and the brightness of the light-emitting diode. -1 2-This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) -------- II ------ ΪΤ ----- i (Please read the back first Please note this page before filling in this page) 4 5 15 0 5 A7 B7 V. Description of the Invention (丨 丨) (Comparative Example 2) For comparison, a method known as M conventional technique was used to grow a single crystal, and the concentration of B in the crystal was Three levels of η-type GaP single crystal substrates with IXIO1 * 1 cii ^ K and different B 澹 degrees. Using the n-type GaP single crystal substrate, an epitaxial gadolinium for GaP yellow-green light-emitting diode was prepared by the above-mentioned process. Thereafter, in the same manner as in Example 2, a GaP light-emitting diode was produced. The B concentration in the η-type GaP single crystal substrate of the obtained GaP yellow-green light-emitting diode epitaxial wafer and the brightness of the light-emitting diode are shown in Fig. 4 together with the results of Example 2. It can be seen from FIG. 4 that the light emitting diode obtained under the condition of η-type (53! &Gt; single crystal substrate with a B 澹 degree of lx 1 0 n C nr * &gt; 最好, preferably 5 X 1 c Μ). In addition, the uneven brightness is that the σηΜ of the GaP yellow-green light emitting diode epitaxial wafer for a GaP yellow-green light-emitting diode at a η-type GaP single crystal substrate at 1X1 〇n ciT1 Μ is 2.27 In contrast, when the concentration of B in the η-type GaP single crystal substrate of the conventional technology is an epitaxial wafer for GaP yellow-green light-emitting diodes on 1 × 10 ~ cn ^ M, it is 6.54. That is, By making the concentration of B in the η-type G a P single crystal substrate to 1 X 1 c af3 M, the brightness unevenness of the epitaxial wafer for GaP yellow-green light-emitting diode can be made smaller. (Example 3) )

Next, an example of a GaP pure green light emitting diode will be described below. The outline of the structure of the epitaxial wafer for GaP yellow-green light-emitting diodes produced in this example is shown in the fifth drawing. In the fifth figure, the 9-series η-type GaP _ 1 3-This paper size applies to the Chinese national standard {CNS} A4 specification (2) 〇 × 297 mm) -------- i ^ ---- --ir ----- 0 (Please read the notes on the back before filling out this page) Du Yinhua, Consumer Work Co-operation, Central Standards Bureau, Ministry of Economic Affairs 4 5 15 0 5 A7 B7 5. Description of the invention () Single crystal substrate, 10 for 11 type 60 buffer layer, 11 傺 sulfur (s) doped GaP epitaxial layer, 12 傜 P type GaP epitaxial layer β as η-type GaP single crystal substrate 9 Using a Te-doped GaP single crystal substrate made by the liquid-encapsulated Cheknowski (LEC) method, the carrier concentration was set to 2 乂 1017 ^ -3, and the main surface was set to (111) 8 planes. First, on this single crystal plate 9, an n-type 60 buffer layer 10 is grown by a conventional liquid phase epitaxial growth method. This n-type GaP buffer layer is used as a Si dopant, and the cut-off concentration is determined as 4 乂 1〇17 «: Hui-3, the layer thickness is set to 60 &gt;« *. A η-type GaP single crystal substrate 9 for growing a 逑 η-type GaP retarded layer 10 is set on the substrate support of the known building-type sliding plate, and it is set as a sulfur (S) doped η-type in the first solution tank. A predetermined amount of 8a gold stellate, GaP polycrystal, and Ga2S3 as the S source are used for the growth solution of the Gap epitaxial layer 11. In the second solution cell, Ga Au and GaP polycrystals are set as a solution for growing the P-type GaP epitaxial layer 12. In a state where the substrate and the growth solution are separated, the slide plate is set in an epitaxial growth furnace, heated to 1000 × 3 under an air flow, and maintained for 1 hour to dissolve Gap polycrystals to a saturated state for the Ga intestine. After that, the substrate holder was hung so that the surface of the n-type GaP buffer metal 10 was in contact with the growth solution of the @th liquid pool, and then cooled to 90 (). 〇, a sulfur (S) -doped η-type Gap epitaxial layer was grown on the n-type Gaf) stab layer 10 to further slide the substrate support at 901 Å, so that the 埯 (㈧ miscellaneous 0-type GW epitaxial layer) The U surface is in contact with the growth solution in the second solution tank, zinc vapor flows in a hydrogen stream, and a predetermined amount of freshness is taken into the growth solution, and then the temperature is slowly cooled to 8D (TC and doped with sulfur (S)). n-type ^? epitaxial layer u -1 4----------------------------- Order (please read the precautions on the back before filling this page) Central Ministry of Economic Affairs Printed by the Employees ’Cooperatives of the 榇 Jun Bureau. 4 5 1 5 0 5 A7 B7 V. Description of the invention (4) P-type GaP epitaxial layer 12 was grown. After the growth was completed, the substrate holder was slid to separate the growth solution, cooled to room temperature and broadcasted. GaP epitaxial crystal Η β for GaP pure green light emission was obtained. According to the third embodiment, the B content in the crystal was reduced by reducing the water content of B 2 0 3 used in the growth of the GaP single crystal, and the B in the crystal was produced. Three levels β of a π-type GaP single crystal substrate having a concentration of lXl0i7cn-3 or less and different β degrees using this η-type GaP single crystal substrate, and GaP was produced by the above process Epitaxy β for edge color luminescence β Then, on the η-type surface and ρ-type surface of the GaP pure edge color light-emitting epitaxial crystal Η, AuGe and AuBe are deposited, heat-treated, and formed by photoetching The η electrode and the p electrode are separated to produce a GaP light-emitting diode. The obtained epitaxial wafer for a GaP pure green light-emitting diode is prepared by incorporating the B concentration in the η-type GaP single crystal substrate. The brightness of the light-emitting diode is shown in Figure 6. (Comparative Example 3) For comparison, a single crystal was grown by a conventional technique, and the B concentration in the crystal was IX 10 17 cht3 or more and the B concentration Three levels of different η-type GaP single-crystal substrates ^ Using this η-type GaP single-crystal substrate, an epitaxial wafer for GaP passive edge color light-emitting diodes was produced by the above-mentioned process. Thereafter, the same procedure as in Example 3 was used to produce GaP light-emitting diodes were obtained. The relationship between the concentration of β in the η-type GaP single crystal substrate of the epitaxial wafer for GaP pure edge color light-emitting diodes and the brightness of the light-emitting diodes was -1 5-this paper scale Applicable to China National Standard (CNS) A4 specification (210X 297 (Li) -------- 1 ------- ΪΤ ----- 0 (Please read the notes on the back before filling this page) Α7 4 5 1 5 Ο 5 Β7 V. Description of the invention (, 4) The results of Example 3 are also shown in Fig. 6. From Fig. 6, it is known that the B concentration in the η-type GaP 箪 crystal substrate is IX 10 η c f3 or less, preferably 5 X 1 0 ie c m. The light-emitting dimers obtained below -3 are bound to have high brightness. In addition, the unevenness in brightness is 0.34 when the epitaxial crystal for GaP pure fiber color light-emitting diodes with a B concentration of lx 1017 cb · 3 or less in the n-type GaP single crystal substrate is 0.34. On the ground, epitaxial crystals for GaP pure edge-emitting light emitting dioscorea with a B concentration of IX ID or more in the conventional η-type GaP single crystal substrate of conventional technology have an 卽 of 0. OU, that is, if η In the GaP single crystal substrate, the B concentration is IX 10 i7cis-3 or less, and the brightness unevenness of the epitaxial crystal for GaP pure edge color light emitting diodes can be reduced. (Embodiment 4) Next, an example of a GaAsP light-emitting diode is described below. The structure of a GaAsP light-emitting diode epitaxial wafer fabricated in this embodiment is schematically shown in FIG. 7. In FIG. 7, 13 series η-type GaP single crystal substrate, 14 傜 η-type GaAsx Pi-χ constitutes the gradient layer, 15 傜 η-type GaAsPx P-χ constitutes a certain layer, and 16 pseudo-Zn diffusion p-type layers. As the η-type GaP single crystal substrate, A Te-doped GaP single crystal substrate made by the liquid-sealed Cheklaussky (LEC) method was used. The carrier concentration was set to 2X10 17 cm-3, and the main surface was set to be away from the (100) plane. &Lt; 11〇 &gt; A face in a direction of 5 °. At a predetermined position of the well-known vapor phase epitaxial reaction 垆, set the above-mentioned η-type GaP single crystal substrate 13 and a quartz container containing Ga metal at a hydrogen flow of 1 6-this paper scale Applicable to China National Standard (CNS) A4 specification (210X297 mm) ---------- 1 ^ ------ ΪΤ ------ line (please read the precautions on the back before filling (This page) Printed by Shellfish Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs 5 --- 4 Printed by Consumer Cooperatives of Central Bureau of Standards, Ministry of Economic Affairs 15 0 5 A7 ___________B7 _ V. Description of the invention (occupation) The quartz container on which the substrate 13 and Ga gold alloy are placed is heated to the specified temperatures. Next, the HCI gas can be connected to the Ga metal surface to flow, and at the same time, M hydrogen Diluted PH3, 43! 13 and 1 ^ 5 diluted with hydrogen were poured into the reaction furnace, and n-type GaAsx was formed on the substrate 13 to form the gradient layer 14. At this time, As was formed to be X from the time when the growth started. = 〇 to the end of the growth) (= 0.35, which is 5 {can be changed continuously, adjust the ratio of MH hydrogen-diluted PZ3 to As \ diluted with hydrogen. Then, Μχ = 0.35 is constant Generally, the ratio of As diluted by hydrogen and As diluted by hydrogen is fixed. On the η-type GaAsx P, _A composition gradient layer 14, η-type GaAsxP ^ is grown to form a certain layer 15. At this time, in the reaction furnace A predetermined amount of O3 gas is introduced, and nitrogen (N) is doped in the η-type GaAsx P ,, x composition constant layer 15. After the growth is completed, the η-type GaAsx P, -x composition slope layer 14 and η-type GaAsx P are grown. The substrate 13 constituting a certain layer 15 is taken out from the reaction furnace, and is formed by diffusing zinc on the surface of the n-type GaAsx (Vx sister to a certain layer 15) in a well-known method. The P-type layer 16 obtains GaAsP orange light-emitting diode epitaxial crystals. Then, the ti-type surface and p-type surface of the obtained GaAsP orange light-emitting diode epitaxial wafer are respectively impregnated with AuGe and AuBe, and heated. After processing, photoetching was performed to form the η electrode and the P electrode, and then the element was separated by K to produce a GaAsP light-emitting diode. The B concentration in the η-type GaP single crystal substrate of the obtained GaAsP orange light-emitting diode epitaxial wafer and the brightness of the light-emitting diode are shown in FIG. 8. -17- This paper size applies to Chinese national standard {CNS &gt; A4 size (210X 297 mm) ------ i ------ ΪΤ ------ m (Please read the note on the back first Please fill in this page again.) Printed by the Central Consumer Bureau of the Ministry of Economic Affairs, Employee Consumer Cooperative. 461505 A7 B7 V. Description of the Invention (4) (Comparative Example 4) For comparison, a single crystal was grown by a conventional technique. The n-type GaP single crystal substrate 3 in which the B concentration is IX 10 37 car3 or more and the B concentration is different is inclined. Using its π-type GaP single crystal substrate ', a GaAsP orange light-emitting diode® epitaxial wafer was prepared by the above-mentioned process. Subsequently, Example 4 was followed to produce a GaAsP light-emitting diode. The obtained GaAsP orange light-emitting diode was fabricated. The concentration of B in the 11 S 6aP single crystal substrate of the epitaxial wafer for body use is pseudo-brightness. The results of Example 4 are also shown in FIG. 8. According to the eighth plaque, the B concentration in the π-type GaP single crystal substrate is less than lx 10 17 cur3, and more preferably 5 × 1016 cm-3. The light-emitting diode obtained is bound to have high brightness. Furthermore, brightness The non-uniformity of an epitaxial wafer for GaAsP orange light-emitting diodes with a degree of IX 10 17 C ·· 3 or lower in an n-type 6aP single crystal substrate is <^-1 at 0.94. In contrast, in When the epitaxial wafer for a GaAsP orange light-emitting diode having a B concentration of IX 10 17 c «r3 or more in the conventional technique 1« type 6 &amp;? single crystal substrate is 2.97, that is, By changing the concentration of B in the n-type GaP single crystal substrate to IX 17 ci3 or less, the brightness unevenness of the epitaxial wafer for GaAsP orange light-emitting diodes can be minimized. (Example 5) AlGaP An example of the case of a light-emitting diode is described below. The outline of the epitaxial ytterbium structure for AlGaP light-emitting diodes produced in this embodiment is shown in Fig. 9. In Fig. 9, 17 is like an n-type GaP single crystal group-1. 8-This paper size is applicable to China National Standards (CNS) A4 size {210X297mm) I- II (Please read the note on the back first (Please fill in this page for the matters needing attention). Line 4 The Central Consumers ’Association of the Ministry of Economic Affairs and the Consumers’ Cooperatives of India 15 0 5 A7 B7 V. Description of the invention (7) Crystal substrate, 18 傜 η Gay, lni_Y P composition slope layer, 19 It is a η-type (Alx Gai_x) y Ιηι.γP coating, 20 like an undoped π-type (Alx Gai_x) y Inn P active layer, 21 like a ρ-type (Alx Ga: L_x) y Ιηι_γ P coating, The 22-type p-type GaAs contact layer e is used as a ii-type GaP single crystal substrate. A Te-doped GaP single crystal substrate made by the liquid-tight Cherkowski (LEC) method is used. The carrier concentration is 2X1G17cb-3. The surface is defined as the surface departing from the (1G0) surface to &lt; 100 &gt; 5β. The n-type GaP single crystal substrate 17 is set in a susceptor of a H0CVD reactor, and the substrate is turned into a hydrogen atmosphere. Warm up to the specified temperature. Using hydrogen as a carrier gas, first supply triffiethyl idium TMI, triiethyl galiuni TMG, phosphorous trihydrogen (PH3 &gt;), and selenized digas (! 1236) as raw material gases. On the n-type GaP single crystal substrate 17, an n-type Gay ΙΠι_γ composition gradient layer β is grown. At this time, the raw material gas is adjusted. The amount of gas supplied to make Ga composition y can be continuously changed from y = 1 at the beginning of growth to y = (U at the end of growth. Next, supply trimethylaluminum (TMA), THI, TMG, PH3 as the raw material gas. , H2Se, an n-type (AlO, 7 Ga0.3.) 0.5 In0.5 P cladding layer 19 is grown on the n-type composition gradient layer 18. Thereafter, TA, TMI, TM6, and Pfl were supplied as source gases, and an undoped (Al0.7 Ga0.8) 0.5 In0.s P active layer 2D was grown on the n-type cladding layer 19. As raw material gases, THA, TMI, TMG, PH3, and dimethyl zinc (DMZ) were grown, and a p-type (AlO.?Ga〇.3) was grown on the undoped active layer 20. 5 Ιη〇.5 Ρ coating layer 21. Finally, as the raw material gas supply THG, trihydrogen B «MAsH3), DMZ, a p-type GaAs bonding layer 22 was grown on the P-type cladding layer 21, and AlGalnP -1 9 ----------- ------- iT ----- 0 (Please read the notes on the reverse side before filling out this page) This paper size applies to China National Standard (CNS) A4 (210X297 mm) Central Bureau of Standards, Ministry of Economic Affairs Printed by Shelley Consumer Cooperatives ^ 15 0 5 A7 B7 V. Description of the invention (,?) Epitaxial wafer for orange light-emitting hawthorn body β In this example, the water content of B2 03 used to reduce the growth of GaP crystals was reduced. Three levels of η-type GaP single-crystal substrates with B-degrees below IX 10 i? C nr3 and different B-flags were prepared using the concentration of B in the crystals ^ This η-type GaP single-crystal substrate was used, and The epitaxial crystal β for A18aInP orange light-emitting diodes was produced by the above process. Then, the n-type and P-type surfaces of the epitaxial wafers for AlGalnP orange light-emitting diodes were obtained, and AuGe and AuBe were respectively deposited, and heat treatment was applied. · Photon etching was used to form the η electrode and the 电极 &gt; electrode, and the element was divided into males to produce an AlGalnP light-emitting diode. 》 The brightness and brightness of the B-concentration light-emitting diode in the η-type GaP single crystal substrate of the obtained epitaxial crystalline AlGalnP orange light-emitting diode are shown in FIG. 10. For comparison, three levels of single crystals of η-type GaP substrates having a B concentration in the crystal of IX 10 17 c «-3 or more and different B concentrations were prepared by conventional techniques. Using its n-type GaP single crystal substrate, the epitaxial crystalline gadolinium for AlGalnP orange light-emitting diodes was fabricated by the above process. Thereafter, in the same manner as in Example 5, an AlGalnP light-emitting dimer was produced. The brightness of the B concentration in the η-type GaP single crystal substrate of the epitaxial wafer for AlGalnP orange light-emitting bismuth body thus obtained was shown in the tenth plaque at the same time as the result of Example 5. On the 10th circle, it was learned that when the B concentration in the η-type GaP single crystal substrate is 1 X 1 D 17 C jr 3 or less, and more preferably 5 X 丨 〇16 or less, the light-emitting dimer obtained is bound to have a high degree. brightness. -20- This paper size is applicable to Chinese National Standard (CNS) Α4 specification (2! 〇 × 297mm) ---.---------------------------- line (Please read first Note on the back page, please fill in this page again) A7 4-51505 _____B7 _ 5. Description of the invention (η) In addition, the uneven brightness is equivalent (β concentration in type 1 GaP single crystal substrate is ixi (/ 7 coT1 Μ When the epitaxial wafer for AlGalnP orange light-emitting diode is used, it is 7.45. Relatively, the concentration of B in the η-type GaP single crystal substrate of the conventional technique is ΙΙΙΟ '&quot; 1 cnf3 W. The epitaxial wafer for AlGalnP orange light-emitting diode At that time, its Ah is 20.9. In other words, if the B concentration in the η-type G a P single crystal substrate can be reduced to 1 X 1 c Μ, the brightness of the epitaxial crystal M for AlGalnP orange light-emitting diodes can be reduced. The uniformity becomes extremely small. [Effect of the invention] As explained above, if the present inventor, according to the present invention, an epitaxial wafer for a light-emitting semi-corporeal element with a higher brightness than conventional ones can be obtained, and the epitaxial wafer M made from the epitaxial crystal M can be obtained. High-brightness light-emitting semiconductor devices. In the conventional case, although large unevenness in brightness occurs between wafers, Those who limit their B-thickness can also reduce the uneven brightness between the wafers. In addition, in the GaAsP-based light-emitting diode epitaxial wafer and the AlGalnP-based light-emitting epitaxial wafer, the temperature can be changed to change the temperature. The same effect can also be obtained at the emission wavelength. In addition, the case where Te is used as the dopant of the η-type G a P single crystal substrate is shown in the case example, but other dopants such as S 丨 and S are used. The same effect can also be obtained at the same time. _The simple explanation of the formula 1 _ is a rough plaque indicating the implementation of the GaP red light-emitting diode structure of 洌 1. _ 2 1 * This paper size applies to China National Standard (CNS) A4 Specifications (210X297 mm): ----- 1 ^ 1-I .---- 1T ------ ^ (Please read the precautions on the back before filling this page) Staff Consumption of Central Bureau of Standards, Ministry of Economic Affairs Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs of the Cooperative Society, printed 15 0 5 A7 _B7_ V. Description of the Invention (X) Figure 2 shows the n-type GaP of the GaP red light-emitting diode of Example 1 and Comparative Example 1. The relationship between B concentration and brightness in a single crystal substrate is shown in Figure 3. Figure 3 shows The schematic diagram of the GaP yellow-green light-emitting diode structure of cell example 2. The fourth line shows the B in the n-type GaP single-crystal substrate of the G a P yellow-green light-emitting diode of the actual picking example 2 and the comparative example. The relationship between the concentration and the brightness is shown in Fig. 5. Fig. 5 is a schematic diagram showing the structure of GaP pure green light-emitting dimer body of the pickled example 3. Fig. 6 is a diagram showing the GaP pure green light-emitting diode 2 of the real cell example 3 and comparative example 3. Relation diagram between B concentration and brightness in an n-type GaP single crystal substrate of a polar body. Fig. 7 is a schematic diagram showing the structure of a GaAsP orange light emitting diode according to the fourth embodiment. The eighth circle indicates the relationship between the B concentration and brightness in the n-type GaP single crystal substrate of the Ga As P orange light-emitting diode of Example 4 and Comparative Example 4. Fig. 9 is a schematic drawing showing the structure of an AlGalnP orange light emitting diode according to the fifth embodiment. Figure 0 is a pseudo graph showing the relationship between the B concentration and the brightness in an n-type GaP single crystal substrate with an AlGalnP orange light-emitting diode of Example 5 and Comparative Example 5. [Explanation of Symbols] -22- This paper size applies to the Chinese National Standard {CNS) A4 specification (210X297 mm)-: ------- install ---: ---- order ----- line (Please read the precautions on the back before filling this page) 451505 A7 B7 V. Description of the invention (㈠) an8 a Cu D1 rt G z 6 G aa Λα ΛαaM type_type type nnpnpnnznn layer ... 1 2M5 7 9 1 In addition, pf plate Ga plate base type base, _. crystal P crystal layer ΪΪ, knotted extension EA5S _ ^ 冲 冲 P and P5P? outer retardation layer extension P &amp; 6 Shaped miscellaneous rubbing layer balance η layer extension XX evening s S p AA ftaa

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Layer-coating coverage Y slope 1. In In group y P I .--.------- install-(Please read the precautions on the back before filling this page) Formless X a 1 6 A (X 隹 1 A 剌 A a doped with iy

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It is suspected to be printed by S Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. This paper size is applicable to China National Standards (CNS) A4 specifications (210X297 mm).

Claims (1)

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Λ8 B8 C8 D8 VI. Patent Application Fanyuan 1. An epitaxial wafer for light-emitting semiconductor elements, which is pseudo-formed on an η-type GaP single crystal substrate, and at least an η-type semiconductor epitaxial layer and p are formed. For the semiconductor epitaxial layer, the boron (B) in the n-type GaP single crystal substrate is IX it) π cm-3 or less. 2. For the epitaxial wafer for light-emitting semiconductor elements, such as in item 1 of the scope of patent application, where: (B) concentration in the above η-type GaP single crystal substrate is 5 × 10ω c * -3 or less. The epitaxial wafer for a light-emitting semiconductor device according to item 1 or item 2, wherein the n-type semiconductor epitaxial layer and the p-type semiconductor epitaxial layer are conventionally composed of GaP. 4. For light-emitting semiconductor devices according to item 1 or 2 of the scope of patent application Epitaxial crystal H, in which the η-type semiconductor epitaxial layer and ρ-type semiconductor epitaxial layer 傜 are composed of GaAsx Pi-x (0 &lt; χ &lt; 1). 5. If the light-emitting semiconductor element of the first or second item of the scope of patent application An epitaxial wafer is used, in which the upper 逑 n-type semiconductor epitaxial layer and the p-type semiconductor epitaxial layer are pseudo-formed by (Alx Gai__x) y Ini_Y P (0 &lt; x &lt; l, 0 &lt; y &lt; l). 6. A light-emitting semiconductor The element pseudo is produced by the epitaxial crystal for light-emitting semiconductor elements in the scope of patent applications No. 1 to 5. -24- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) J-- „ ----- 1 ^-^ -----, w ------ 0 (Please read the note on the back first Matters then fill out this page)