WO2012164827A1 - Vapor phase epitaxy method and light emitting element substrate manufacturing method - Google Patents

Vapor phase epitaxy method and light emitting element substrate manufacturing method Download PDF

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Publication number
WO2012164827A1
WO2012164827A1 PCT/JP2012/003001 JP2012003001W WO2012164827A1 WO 2012164827 A1 WO2012164827 A1 WO 2012164827A1 JP 2012003001 W JP2012003001 W JP 2012003001W WO 2012164827 A1 WO2012164827 A1 WO 2012164827A1
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vapor phase
layer
phase growth
substrate
compound semiconductor
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French (fr)
Japanese (ja)
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実 川原
智弘 秋山
和慶 西山
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信越半導体株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H01L33/0062—Processes for devices with an active region comprising only III-V compounds
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/16—Controlling or regulating
    • C30B25/165—Controlling or regulating the flow of the reactive gases
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/18—Epitaxial-layer growth characterised by the substrate
    • C30B25/186—Epitaxial-layer growth characterised by the substrate being specially pre-treated by, e.g. chemical or physical means
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/44—Gallium phosphide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02387—Group 13/15 materials
    • H01L21/02395—Arsenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02439—Materials
    • H01L21/02455—Group 13/15 materials
    • H01L21/02463—Arsenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02538—Group 13/15 materials
    • H01L21/02543—Phosphides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/0257—Doping during depositing
    • H01L21/02573—Conductivity type
    • H01L21/02576—N-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/0257—Doping during depositing
    • H01L21/02573—Conductivity type
    • H01L21/02579—P-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD

Definitions

  • the present invention relates to a method for forming a compound semiconductor layer, and more particularly to a vapor phase growth method for growing a compound semiconductor layer on a substrate by a hydride vapor phase growth method and a method for manufacturing a substrate for a light emitting element.
  • a light-emitting element in which a light-emitting layer and a current diffusion layer are formed on a GaAs single crystal substrate is known.
  • a composition formula (Al x Ga 1-x ) y In 1-y P (provided that metal organic vapor phase phase epitaxy method, hereinafter simply referred to as MOVPE method) is used.
  • MOVPE method metal organic vapor phase phase epitaxy method
  • a light-emitting element in which a layer and a current diffusion layer (also referred to as a window layer) made of GaP are formed is known.
  • this GaP current diffusion layer As a method for forming this GaP current diffusion layer, after a relatively thin connection layer is formed on the light emitting layer side by MOVPE method, it is relatively thick by hydride vapor phase epitaxy method (hereinafter referred to simply as HVPE method).
  • HVPE method hydride vapor phase epitaxy method
  • the light emitted from the light emitting layer of such a light emitting element toward the substrate is absorbed by the GaAs substrate which is a growth substrate. Therefore, in order to extract the light emitted to the substrate side, the GaAs substrate is removed by wet etching, and a GaP current transparent to the light is formed on the surface of the light emitting layer on the side where the GaAs substrate is removed.
  • a technique for increasing the brightness of a manufactured light-emitting element by growing a diffusion layer (second current diffusion layer) is also conventionally known.
  • the growth rate of GaP on the surface of the light emitting layer on the side where the GaAs substrate has been removed varies, and as a result, the thickness of the GaP layer varies greatly between batches, and this is a defect in a light emitting device or the like manufactured thereafter. It has become a problem that it becomes the cause of this and becomes a big cause to reduce the yield.
  • the variation in the growth rate of GaP is caused by the growth of the GaP layer depending on the degree of deposition of GaP due to the source gas as shown in FIG. 3B on a member other than the substrate in the HVPE growth apparatus, for example, the susceptor. It is because it is inhibited.
  • the present invention has been made in view of such problems of the conventional method, and a hydride vapor phase growth method capable of suppressing the number of GaP deposited by a raw material gas on members other than the substrate in the HVPE growth apparatus, and
  • An object of the present invention is to provide a method for manufacturing a substrate for a light-emitting element capable of making the film thickness of an n-type GaP layer, which is a second current diffusion layer, uniform between batches.
  • the present invention provides a vapor phase growth method for epitaxially growing a III-V compound semiconductor layer on a substrate in a vapor phase growth apparatus by a hydride vapor phase growth method.
  • a vapor phase growth method characterized in that during the epitaxial growth of a group compound semiconductor layer, the epitaxial growth is interrupted at least once and gas etching in the vapor phase growth apparatus is performed.
  • the deposit can be removed by gas etching at a stage where the size of the deposit of the source gas generated on the susceptor or the like in the vapor phase growth apparatus is small, it is always possible to achieve epitaxial growth by this deposit.
  • the III-V compound semiconductor layer can be epitaxially grown while the influence is suppressed. Further, this makes the growth rate of each group III-V compound semiconductor layer uniform between batches, and as a result, variation in the thickness of each group III-V compound semiconductor layer between batches can be surely reduced. .
  • the gas etching in the vapor phase growth apparatus is performed twice or more during the epitaxial growth of the III-V compound semiconductor layer.
  • the group III-V compound semiconductor layer can be epitaxially grown while removing the deposits of the source gas generated on the member such as the susceptor in the vapor phase growth apparatus more efficiently.
  • HCl gas used as a source gas in a general hydride vapor phase growth method is used as an etching gas, the epitaxial growth of the III-V compound semiconductor layer and the gas etching in the vapor phase growth apparatus can be further performed. Can be done efficiently.
  • the III-V compound semiconductor layer can be a GaP layer.
  • a GaP layer is suitable as the III-V compound semiconductor layer in the hydride vapor phase growth method of the present invention.
  • an n-type cladding layer and an active layer made of (Al x Ga 1-x ) y In 1-y P (where 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1) are formed on an n-type GaAs substrate.
  • a step of forming a light emitting layer by sequentially stacking a p-type cladding layer, a step of stacking a p-type GaP layer as a first current diffusion layer on the light emitting layer, and etching the n-type GaAs substrate.
  • the n-type GaP layer is laminated on the surface of the light emitting layer on the side where the n-type GaAs substrate is removed by the vapor phase growth method.
  • a method for manufacturing a substrate for a light emitting device is provided. .
  • an n-type GaP layer made of GaP having a lattice constant different from that of GaAs is formed on the light-emitting layer lattice-matched to GaAs of the n-type GaAs substrate.
  • the growth rate of the n-type GaP layer between batches can be made uniform, whereby the n-type GaP layer between batches can be made uniform.
  • the thickness variation can be surely reduced, and a high-quality light-emitting element substrate can be manufactured without reducing the yield.
  • the III-V group compound semiconductor layer is epitaxially grown in a state in which the influence of the deposition of the source gas generated on the susceptor or the like in the vapor phase growth apparatus on the epitaxial growth is reliably suppressed. It can be performed. Further, this makes the growth rate of each group III-V compound semiconductor layer uniform between batches, which can surely reduce the variation in the thickness of each group III-V compound semiconductor layer between batches. .
  • an n-type GaP layer made of GaP having a lattice constant different from that of GaAs is laminated on the light-emitting layer lattice-matched to GaAs on the n-type GaAs substrate.
  • the growth rate of the n-type GaP layer between batches can be made uniform, whereby the thickness of the n-type GaP layer between batches can be made uniform. It is possible to manufacture a high-quality light-emitting element substrate without reducing the variation in thickness and reducing the yield.
  • the GaAs substrate is removed by wet etching to extract the light emitted from the light emitting layer to the substrate side, and the light emission is performed.
  • Conventionally known is a method of growing a GaP current diffusion layer that is transparent to light on the surface of the layer from which the GaAs substrate has been removed.
  • an n-type GaP layer made of GaP having a lattice constant different from that of GaAs must be grown on a light-emitting layer lattice-matched to GaAs, which is the material of the n-type GaAs substrate. For this reason, it is difficult to grow a GaP layer under such conditions, and it is easily affected by disturbance factors such as deposition of a source gas generated in a member such as a susceptor in a vapor phase growth apparatus. This causes a variation in the growth rate of the GaP layer, that is, the thickness of the GaP layer, which causes a defect in a light emitting device manufactured thereafter, and causes a large decrease in yield.
  • the present inventors have conducted intensive studies, and as a result, the epitaxial growth was interrupted at least once while the III-V compound semiconductor layer was epitaxially grown on the substrate by hydride vapor phase epitaxy. Then, by performing gas etching in the vapor phase growth apparatus, it was found that the deposition of the source gas generated in a member such as a susceptor can be suppressed and the variation in the thickness of the GaP layer can be reduced, and the present invention has been completed.
  • FIG. 1 shows a barrel type vapor phase growth apparatus
  • the vapor phase growth method of the present invention can be applied to other vapor phase growth apparatuses such as a horizontal type and a vertical type. is there.
  • the vapor phase growth apparatus 1 includes a group III metal compound generation tube 3 for generating a group III metal compound inside the chamber 2.
  • This group III metal compound production tube 3 has a reservoir 4 in which a group III metal is mounted.
  • the group III metal compound production tube 3 is heated by the first heater 5.
  • the ratio of the mixture of these metals may be adjusted and mounted on the reservoir 4.
  • the vapor phase growth apparatus 1 further includes a group V element introduction pipe (not shown) for introducing a group V element, a rotatable susceptor 6 on which the substrate W is placed, and a gas discharge pipe (not shown) for discharging various gases. And a second heater 7 for heating the substrate W.
  • the III-V compound semiconductor layer is epitaxially grown as follows.
  • the substrate W is prepared and placed on the susceptor 6 in the vapor phase growth apparatus 1.
  • the substrate W is not particularly limited.
  • a III-V group compound semiconductor substrate such as GaAs, GaN, or GaP can be used.
  • III-V compound semiconductor layer is epitaxially grown on the substrate W by hydride vapor phase epitaxy.
  • III-V group compound semiconductor layer is not particularly limited, but can be, for example, a GaP layer.
  • the group III element metal Ga in the HVPE apparatus 1 is III.
  • the reaction of the following formula (1) GaCl is generated and supplied onto the substrate W together with H 2 gas which is a carrier gas.
  • the epitaxial growth temperature is set to, for example, 640 ° C. or more and 860 ° C. or less.
  • P which is a group V element supplies PH 3 (phosphine) onto the substrate together with H 2 which is a carrier gas.
  • GaP is produced
  • the epitaxial growth is interrupted at least once, preferably two times or more, more preferably five times or more, and gas etching in the vapor phase growth apparatus 1 is performed.
  • the timing for performing the gas etching is not particularly limited, but the first half of the epitaxial growth, which is a stage in which the number of precipitates generated in the member such as the susceptor 6 in the vapor phase growth apparatus 1 is relatively small and the size is relatively small. It is preferable to carry out in the part.
  • the gas etching is performed twice or more, it is preferable to perform the next gas etching at a stage where the number of precipitates generated again after performing the gas etching once is relatively small and the size is relatively small. In this way, it is possible to more effectively suppress the influence on the epitaxial growth due to the deposit of the source gas.
  • a method of performing gas etching in the vapor phase growth apparatus 1 during the epitaxial growth of the III-V group compound semiconductor layer first, as an epitaxial growth process, for example, a material is supplied under the gas supply conditions as shown in FIG. A gas and a carrier gas are supplied into the vapor phase growth apparatus 1, and the III-V compound semiconductor layer is epitaxially grown for a certain time (for example, 1 hour) by the above method.
  • the gas supply conditions are switched to the conditions shown in FIG. 1B, for example, and the gas etching in the vapor phase growth apparatus 1 is performed in a shorter processing time (for example, 3 minutes) than the epitaxial growth process. Do.
  • the III-V compound can be removed while removing the deposits of the source gas generated on the member such as the susceptor 6 in the vapor phase growth apparatus 1 more efficiently. This is preferable because the semiconductor layer can be epitaxially grown.
  • the general hydride vapor phase growth method uses HCl gas as a source gas. It is preferable because epitaxial growth of the semiconductor layer and gas etching in the vapor phase growth apparatus 1 can be performed more efficiently.
  • HCl gas is used as a group III metal as shown in FIG. Since it suffices that the metal Ga mounted on the reservoir 4 of the compound generation tube 3 is not brought into contact with the reservoir 4, it is very simple and efficient.
  • an n-type GaAs substrate 110 is prepared as a growth substrate, cleaned, and then placed in a MOVPE reactor, and an n-type GaAs buffer layer 120 is formed on the n-type GaAs substrate 110 by 0.1 to 1 Epitaxial growth is performed.
  • Step 2 (Al x Ga 1-x ) y In 1-y P (where 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ ) is formed on the n-type GaAs buffer layer 120 as the light emitting layer 130. 1), an n-type cladding layer 131 having a thickness of 0.8 to 4.0 ⁇ m, an active layer 132 having a thickness of 0.4 to 2.0 ⁇ m, and a p-type cladding layer 133 having a thickness of 0.8 to 4.0 ⁇ m. Are epitaxially grown in this order.
  • each layer is performed by a known MOVPE method.
  • source gas used as each component source of Al, Ga, In, and P
  • Al source gas trimethylaluminum (TMAl), triethylaluminum (TEAl), etc.
  • Ga source gas trimethylgallium (TMGa), triethylgallium (TEGa), etc.
  • In source gas trimethylindium (TMIn), triethylindium (TEIn), etc.
  • P source gas trimethyl phosphorus (TMP), triethyl phosphorus (TEP), phosphine (PH 3 ), etc.
  • dopant gas trimethyl phosphorus (TMP), triethyl phosphorus (TEP), phosphine (PH 3 ), etc.
  • P-type dopant Mg source biscyclopentadienyl magnesium (Cp 2 Mg), etc.
  • Zn source dimethyl zinc (DMZn), diethyl zinc (DEZn), etc.
  • N-type dopant Si source silicon hydride such as monosilane.
  • Step 3 a GaP connection layer 140 having a thickness of 0.05 to 2.0 ⁇ m is grown on the p-type cladding layer 133 by the MOVPE method, and further, a thickness serving as a first current diffusion layer is formed thereon.
  • a p-type GaP layer 150 of 5 ⁇ m to 200 ⁇ m is epitaxially grown by HVPE. Also in the epitaxial growth of the first current diffusion layer by the HVPE method, the vapor phase growth method of the present invention in which gas etching is performed in the middle can be applied.
  • Step 4 the n-type GaAs substrate 110 and the n-type GaAs buffer layer 120 are removed by etching or the like.
  • step 5 the n-type GaP layer 160, which is the second current diffusion layer, is epitaxially grown on the n-type cladding layer 131 exposed by the removal of the n-type GaAs substrate by the HVPE method. To manufacture.
  • the epitaxial growth is interrupted at least once, preferably twice or more, more preferably five times or more during the epitaxial growth of the n-type GaP layer 160.
  • the n-type GaP layer 160 is epitaxially grown while performing gas etching in the vapor phase growth apparatus.
  • the gas phase Since the deposits of the source gas generated in the susceptor and other members are removed by gas etching in the growth apparatus, they are not easily affected by such deposits. As a result, the growth rate of the n-type GaP layer between batches can be made uniform, and thus the variation in the thickness of the n-type GaP layer between batches can be reliably reduced, and high quality can be achieved without reducing the yield.
  • a substrate for a light emitting element can be manufactured.
  • n-type GaAs single crystal substrate having a thickness of 200 ⁇ m is prepared, an n-type GaAs buffer layer is epitaxially grown on each of the substrates by 0.5 ⁇ m, and a light emitting layer (Al 0.85 Ga 0 is formed on the n-type GaAs buffer layer. .15 ) 0.45 In 0.55 P n-type cladding layer (1.0 ⁇ m), (Al 0.1 Ga 0.9 ) 0.45 In 0.55 P active layer (0.6 ⁇ m) ), P-type cladding layer (1.0 ⁇ m) made of (Al 0.85 Ga 0.15 ) 0.45 In 0.55 P was laminated in this order by the MOVPE method.
  • a p-type GaP layer as a first current diffusion layer was grown on the p-type cladding layer.
  • the p-type GaP layer was formed to a thickness of 100 ⁇ m by the HVPE method after forming a 2.0 ⁇ m-thick p-type GaP connection layer on the light emitting layer side by the MOVPE method.
  • the n-type GaAs single crystal substrate is removed by wet etching, and an n-type GaP layer as a second current diffusion layer is formed on the surface of the light emitting layer on the side where the n-type GaAs single crystal substrate is removed.
  • Such a light emitting element substrate was manufactured five times (5 batches).
  • the number of batches in this example was 10.
  • the number of GaP deposited on the susceptor in each batch is a number even after 4 hours have passed since the epitaxial growth of the n-type GaP layer was started.
  • the size was relatively small.
  • the number of GaP deposited on the susceptor in each batch is 150 to 200 in 3 hours after the epitaxial growth of the n-type GaP layer is started.
  • the size was relatively large.
  • the epitaxial growth is interrupted at least once during the epitaxial growth. It can be seen that by performing the gas etching inside, the group III-V compound semiconductor layer can be epitaxially grown in a state where the influence of the precipitates on the member such as the susceptor in the vapor phase growth apparatus on the epitaxial growth is suppressed. This also shows that the growth rate of each group III-V compound semiconductor layer between batches is made uniform, and this makes it possible to reliably reduce the variation in thickness of each group III-V compound semiconductor layer between batches.

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Abstract

The present invention is a vapor phase epitaxy method whereby a group III-V compound semiconductor layer is epitaxially formed upon a substrate within a vapor phase epitaxy device by a hydride vapor phase epitaxy method. During epitaxial growth of the group III-V compound semiconductor layer, at least one iteration of the epitaxial growth is interrupted and gas etching is carried out within the vapor phase epitaxy device. It is thus possible to control a GaP deposition number by raw gas to a member other than a substrate within an HVPE growth device.

Description

気相成長方法及び発光素子用基板の製造方法Vapor growth method and method for manufacturing substrate for light emitting device
　本発明は、化合物半導体層の形成方法に関し、特にハイドライド気相成長法で基板上に化合物半導体層を成長させる気相成長方法及び発光素子用基板の製造方法に関する。 The present invention relates to a method for forming a compound semiconductor layer, and more particularly to a vapor phase growth method for growing a compound semiconductor layer on a substrate by a hydride vapor phase growth method and a method for manufacturing a substrate for a light emitting element.
　従来、ＧａＡｓ単結晶基板上に、発光層と電流拡散層とを形成した発光素子が知られている。
　例えばｎ型ＧａＡｓ単結晶基板上に、有機金属気相成長法（Ｍｅｔａｌ　Ｏｒｇａｎｉｃ　Ｖａｐｏｒ　Ｐｈａｓｅ　Ｅｐｉｔａｘｙ法、以下単にＭＯＶＰＥ法という）により組成式（ＡｌｘＧａ１－ｘ）ｙＩｎ１－ｙＰ（ただし、０≦ｘ≦１，０≦ｙ≦１）にて表される化合物にて各々構成されたｎ型クラッド層、活性層、ｐ型クラッド層がこの順序で積層されたダブルへテロ構造からなる発光層と、ＧａＰからなる電流拡散層（窓層とも言う）を形成した発光素子が知られている。 Conventionally, a light-emitting element in which a light-emitting layer and a current diffusion layer are formed on a GaAs single crystal substrate is known.
For example, on an n-type GaAs single crystal substrate, a composition formula (Al x Ga 1-x ) y In 1-y P (provided that metal organic vapor phase phase epitaxy method, hereinafter simply referred to as MOVPE method) is used. Light emission having a double hetero structure in which an n-type cladding layer, an active layer, and a p-type cladding layer each composed of a compound represented by 0 ≦ x ≦ 1, 0 ≦ y ≦ 1) are stacked in this order. A light-emitting element in which a layer and a current diffusion layer (also referred to as a window layer) made of GaP are formed is known.
　このＧａＰ電流拡散層を形成する方法として、発光層側にＭＯＶＰＥ法により比較的薄く接続層を形成した後に、ハイドライド気相成長法（Ｈｙｄｒｉｄｅ　Ｖａｐｏｒ　Ｐｈａｓｅ　Ｅｐｉｔａｘｙ法、以下単にＨＶＰＥ法という）により比較的厚く第一の電流拡散層を形成する方法が、例えば特許文献１等に開示されている。 As a method for forming this GaP current diffusion layer, after a relatively thin connection layer is formed on the light emitting layer side by MOVPE method, it is relatively thick by hydride vapor phase epitaxy method (hereinafter referred to simply as HVPE method). A method of forming the first current diffusion layer is disclosed in, for example, Patent Document 1 and the like.
　また、このような発光素子の発光層から放たれた基板側への光は、成長用基板であるＧａＡｓ基板により吸収されてしまう。そこでこの基板側へ放出される光を取り出すために、前記ＧａＡｓ基板を湿式エッチングにより除去して、前記発光層の、前記ＧａＡｓ基板が除去された側の表面に、光に対して透明なＧａＰ電流拡散層（第二の電流拡散層）を成長することにより、製造される発光素子の高輝度化を図る技術も従来知られている。 Further, the light emitted from the light emitting layer of such a light emitting element toward the substrate is absorbed by the GaAs substrate which is a growth substrate. Therefore, in order to extract the light emitted to the substrate side, the GaAs substrate is removed by wet etching, and a GaP current transparent to the light is formed on the surface of the light emitting layer on the side where the GaAs substrate is removed. A technique for increasing the brightness of a manufactured light-emitting element by growing a diffusion layer (second current diffusion layer) is also conventionally known.
米国特許　５，００８，７１８号公報US Patent No. 5,008,718
　しかしながら、前記発光層の、前記ＧａＡｓ基板が除去された側の表面へのＧａＰの成長速度がバラツキ、その結果ＧａＰ層の厚さがバッチ間で大きくバラツキ、これがその後製造される発光素子等の不良の原因となり、歩留まりを落とす大きな原因となることが問題となっていた。このＧａＰの成長速度のバラツキは、ＨＶＰＥ成長装置内の基板以外の部材、例えばサセプタ上に図３（ｂ）に示すような原料ガスによるＧａＰの析出が生じると、その程度によりＧａＰ層の成長が阻害されるために生じるものである。 However, the growth rate of GaP on the surface of the light emitting layer on the side where the GaAs substrate has been removed varies, and as a result, the thickness of the GaP layer varies greatly between batches, and this is a defect in a light emitting device or the like manufactured thereafter. It has become a problem that it becomes the cause of this and becomes a big cause to reduce the yield. The variation in the growth rate of GaP is caused by the growth of the GaP layer depending on the degree of deposition of GaP due to the source gas as shown in FIG. 3B on a member other than the substrate in the HVPE growth apparatus, for example, the susceptor. It is because it is inhibited.
　また、ＧａＰのサセプタ上の析出数と、基板上のＧａＰ層の成長速度との間には図２に示すような相関があり、ＧａＰの析出数が多いと基板上のＧａＰ層の成長速度が遅くなり、逆に析出数が少ないと基板上のＧａＰ層の成長速度が速くなることが分かっているが、このＧａＰの析出数を制御する方法は従来知られていなかった。 Further, there is a correlation as shown in FIG. 2 between the number of GaP precipitates on the susceptor and the growth rate of the GaP layer on the substrate, and when the number of GaP precipitation is large, the growth rate of the GaP layer on the substrate increases. On the contrary, it is known that when the number of precipitations is small, the growth rate of the GaP layer on the substrate increases, but a method for controlling the number of GaP precipitations has not been known.
　本発明はこのような従来方法の問題点に鑑みてなされたものであり、ＨＶＰＥ成長装置内の基板以外の部材への原料ガスによるＧａＰの析出数を抑制することができるハイドライド気相成長方法及び、第二の電流拡散層であるｎ型ＧａＰ層の膜厚をバッチ間において均一化することができる発光素子用基板の製造方法を提供することを目的とする。 The present invention has been made in view of such problems of the conventional method, and a hydride vapor phase growth method capable of suppressing the number of GaP deposited by a raw material gas on members other than the substrate in the HVPE growth apparatus, and An object of the present invention is to provide a method for manufacturing a substrate for a light-emitting element capable of making the film thickness of an n-type GaP layer, which is a second current diffusion layer, uniform between batches.
　上記目的を達成するために、本発明では、気相成長装置内で基板上に、ＩＩＩ－Ｖ族化合物半導体層をハイドライド気相成長法によってエピタキシャル成長させる気相成長方法であって、前記ＩＩＩ－Ｖ族化合物半導体層のエピタキシャル成長途中に、少なくとも１回該エピタキシャル成長を中断して前記気相成長装置内のガスエッチングを行うことを特徴とする気相成長方法を提供する。 In order to achieve the above object, the present invention provides a vapor phase growth method for epitaxially growing a III-V compound semiconductor layer on a substrate in a vapor phase growth apparatus by a hydride vapor phase growth method. Provided is a vapor phase growth method characterized in that during the epitaxial growth of a group compound semiconductor layer, the epitaxial growth is interrupted at least once and gas etching in the vapor phase growth apparatus is performed.
　このようにすれば、気相成長装置内のサセプタ等の部材に生じる原料ガスの析出物の大きさが小さい段階において、該析出物をガスエッチングにより除去できるため、常にこの析出物によるエピタキシャル成長への影響を抑制した状態で前記ＩＩＩ－Ｖ族化合物半導体層のエピタキシャル成長を行うことができる。
　さらにこれによって、バッチ間における各ＩＩＩ－Ｖ族化合物半導体層の成長速度を均一なものとし、その結果バッチ間における各ＩＩＩ－Ｖ族化合物半導体層の厚さのバラツキを確実に低減することができる。 In this way, since the deposit can be removed by gas etching at a stage where the size of the deposit of the source gas generated on the susceptor or the like in the vapor phase growth apparatus is small, it is always possible to achieve epitaxial growth by this deposit. The III-V compound semiconductor layer can be epitaxially grown while the influence is suppressed.
Further, this makes the growth rate of each group III-V compound semiconductor layer uniform between batches, and as a result, variation in the thickness of each group III-V compound semiconductor layer between batches can be surely reduced. .
　またこのとき、前記気相成長装置内のガスエッチングを、前記ＩＩＩ－Ｖ族化合物半導体層のエピタキシャル成長途中に２回以上行うことが好ましい。 At this time, it is preferable that the gas etching in the vapor phase growth apparatus is performed twice or more during the epitaxial growth of the III-V compound semiconductor layer.
　このようにすれば、より確実に前記気相成長装置内のサセプタ等の部材に生じる原料ガスの析出物を除去することができ、これによってバッチ間における前記ＩＩＩ－Ｖ族化合物半導体層の成長速度をより均一なものとし、バッチ間における前記ＩＩＩ－Ｖ族化合物半導体層の厚さのバラツキをより確実に低減することができる。 In this way, it is possible to more reliably remove the deposits of the source gas generated on the member such as the susceptor in the vapor phase growth apparatus, and thereby the growth rate of the III-V compound semiconductor layer between batches. And the variation in the thickness of the III-V compound semiconductor layer between batches can be more reliably reduced.
　またこのとき、前記ＩＩＩ－Ｖ族化合物半導体層のエピタキシャル成長途中に、前記気相成長装置内のガスエッチングを行う方法として、前記ＩＩＩ－Ｖ族化合物半導体層をエピタキシャル成長させるエピタキシャル成長工程と、該エピタキシャル成長工程よりも処理時間の短い、前記気相成長装置内のガスエッチング工程と、を交互に繰り返すことができる。 At this time, as a method of performing gas etching in the vapor phase growth apparatus during the epitaxial growth of the III-V compound semiconductor layer, an epitaxial growth step of epitaxially growing the III-V compound semiconductor layer, and Also, the gas etching process in the vapor phase growth apparatus having a short processing time can be alternately repeated.
　このようにすれば、より効率的に前記気相成長装置内のサセプタ等の部材に生じる原料ガスの析出物を除去しながら前記ＩＩＩ－Ｖ族化合物半導体層をエピタキシャル成長させることができるため好ましい。 This is preferable because the group III-V compound semiconductor layer can be epitaxially grown while removing the deposits of the source gas generated on the member such as the susceptor in the vapor phase growth apparatus more efficiently.
　またこのとき、前記気相成長装置内のガスエッチングを、ＨＣｌガスを用いて行うことが好ましい。 At this time, it is preferable to perform gas etching in the vapor phase growth apparatus using HCl gas.
　このようにすれば、一般的なハイドライド気相成長法において原料ガスとして用いられるＨＣｌガスをエッチングガスとして用いるため、前記ＩＩＩ－Ｖ族化合物半導体層のエピタキシャル成長と気相成長装置内のガスエッチングをより効率的に行うことができる。 In this way, since HCl gas used as a source gas in a general hydride vapor phase growth method is used as an etching gas, the epitaxial growth of the III-V compound semiconductor layer and the gas etching in the vapor phase growth apparatus can be further performed. Can be done efficiently.
　またこのとき、前記ＩＩＩ－Ｖ族化合物半導体層をＧａＰ層とすることができる。 At this time, the III-V compound semiconductor layer can be a GaP layer.
　このように、本発明のハイドライド気相成長方法における前記ＩＩＩ－Ｖ族化合物半導体層としては、ＧａＰ層が好適である。 Thus, a GaP layer is suitable as the III-V compound semiconductor layer in the hydride vapor phase growth method of the present invention.
　また、本発明では、ｎ型ＧａＡｓ基板上に（ＡｌｘＧａ１－ｘ）ｙＩｎ１－ｙＰ（ただし、０≦ｘ≦１，０≦ｙ≦１）からなるｎ型クラッド層、活性層、ｐ型クラッド層を順次積層することによって発光層を形成する工程と、該発光層上に第一の電流拡散層であるｐ型ＧａＰ層を積層する工程と、前記ｎ型ＧａＡｓ基板をエッチングにより除去する工程と、前記発光層の、前記ｎ型ＧａＡｓ基板が除去された側の表面に第二の電流拡散層であるｎ型ＧａＰ層を積層する工程と、を有する発光素子用基板の製造方法であって、前記ｎ型ＧａＰ層の積層工程において、上記の気相成長方法によって、前記発光層の、前記ｎ型ＧａＡｓ基板が除去された側の表面にｎ型ＧａＰ層を積層することを特徴とする発光素子用基板の製造方法を提供する。 In the present invention, an n-type cladding layer and an active layer made of (Al x Ga 1-x ) y In 1-y P (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 1) are formed on an n-type GaAs substrate. A step of forming a light emitting layer by sequentially stacking a p-type cladding layer, a step of stacking a p-type GaP layer as a first current diffusion layer on the light emitting layer, and etching the n-type GaAs substrate. And a step of laminating an n-type GaP layer as a second current diffusion layer on the surface of the light-emitting layer on the side where the n-type GaAs substrate is removed. In the step of laminating the n-type GaP layer, the n-type GaP layer is laminated on the surface of the light emitting layer on the side where the n-type GaAs substrate is removed by the vapor phase growth method. A method for manufacturing a substrate for a light emitting device is provided. .
　このような発光素子用基板の製造方法におけるｎ型ＧａＰ層の積層工程において、ｎ型ＧａＡｓ基板のＧａＡｓに格子整合された発光層上に、ＧａＡｓと格子定数の異なるＧａＰからなるｎ型ＧａＰ層を積層する場合であっても、本発明の気相成長方法を用いることにより、バッチ間における前記ｎ型ＧａＰ層の成長速度を均一にすることができ、これによってバッチ間における前記ｎ型ＧａＰ層の厚さのバラツキを確実に低減し、歩留まりを落とすことなく高品質な発光素子用基板を製造することができる。 In the stacking process of the n-type GaP layer in such a method for manufacturing a substrate for a light-emitting element, an n-type GaP layer made of GaP having a lattice constant different from that of GaAs is formed on the light-emitting layer lattice-matched to GaAs of the n-type GaAs substrate. Even in the case of stacking, by using the vapor phase growth method of the present invention, the growth rate of the n-type GaP layer between batches can be made uniform, whereby the n-type GaP layer between batches can be made uniform. The thickness variation can be surely reduced, and a high-quality light-emitting element substrate can be manufactured without reducing the yield.
　以上説明したように、本発明は、気相成長装置内のサセプタ等の部材に生じる原料ガスの析出物の、エピタキシャル成長への影響を確実に抑制した状態で前記ＩＩＩ－Ｖ族化合物半導体層のエピタキシャル成長を行うことができる。
　さらにこれによって、バッチ間における各ＩＩＩ－Ｖ族化合物半導体層の成長速度を均一なものとし、これによってバッチ間における各ＩＩＩ－Ｖ族化合物半導体層の厚さのバラツキを確実に低減することができる。
　また、発光素子用基板の製造方法におけるｎ型ＧａＰ層の積層工程において、ｎ型ＧａＡｓ基板のＧａＡｓに格子整合された発光層上に、ＧａＡｓと格子定数の異なるＧａＰからなるｎ型ＧａＰ層を積層する場合であっても、本発明の気相成長方法を用いることにより、バッチ間における前記ｎ型ＧａＰ層の成長速度を均一にすることができ、これによってバッチ間における前記ｎ型ＧａＰ層の厚さのバラツキを確実に低減し、歩留まりを落とすことなく高品質な発光素子用基板を製造することができる。 As described above, according to the present invention, the III-V group compound semiconductor layer is epitaxially grown in a state in which the influence of the deposition of the source gas generated on the susceptor or the like in the vapor phase growth apparatus on the epitaxial growth is reliably suppressed. It can be performed.
Further, this makes the growth rate of each group III-V compound semiconductor layer uniform between batches, which can surely reduce the variation in the thickness of each group III-V compound semiconductor layer between batches. .
In the step of laminating the n-type GaP layer in the method for manufacturing a substrate for light-emitting elements, an n-type GaP layer made of GaP having a lattice constant different from that of GaAs is laminated on the light-emitting layer lattice-matched to GaAs on the n-type GaAs substrate. Even in this case, by using the vapor phase growth method of the present invention, the growth rate of the n-type GaP layer between batches can be made uniform, whereby the thickness of the n-type GaP layer between batches can be made uniform. It is possible to manufacture a high-quality light-emitting element substrate without reducing the variation in thickness and reducing the yield.
本発明に係るハイドライド気相成長方法を適応できるハイドライド気相成長装置の概略断面図及びガスフローの一例を示した図である。It is the figure which showed the schematic sectional drawing and the example of gas flow of the hydride vapor phase growth apparatus which can apply the hydride vapor phase growth method which concerns on this invention. 気相成長装置内でサセプタ上に生じるＧａＰの析出数と、基板上のＧａＰ層の膜厚との相関を示した図である。It is the figure which showed the correlation with the precipitation number of GaP which arises on a susceptor within a vapor phase growth apparatus, and the film thickness of the GaP layer on a board | substrate. 本発明及び従来方法において、サセプタ上に時間経過と共に生じる原料ガスの析出物の様子を示した概略図である。It is the schematic which showed the mode of the deposit of the raw material gas which arises on a susceptor with time in this invention and the conventional method. 本発明の発光素子用基板の製造方法の工程フローの一例を示した図である。It is the figure which showed an example of the process flow of the manufacturing method of the board | substrate for light emitting elements of this invention.
　前述したように、特許文献１等に記載されている方法によって製造された発光素子において、発光層から基板側へ放出される光を取り出すために、ＧａＡｓ基板を湿式エッチングにより除去して、前記発光層の、前記ＧａＡｓ基板が除去された側の表面に、光に対して透明なＧａＰ電流拡散層を成長する方法が従来知られている。 As described above, in the light emitting device manufactured by the method described in Patent Document 1 or the like, the GaAs substrate is removed by wet etching to extract the light emitted from the light emitting layer to the substrate side, and the light emission is performed. Conventionally known is a method of growing a GaP current diffusion layer that is transparent to light on the surface of the layer from which the GaAs substrate has been removed.
　しかしながら、このような方法においては、ｎ型ＧａＡｓ基板の材料であるＧａＡｓに格子整合した発光層上に、ＧａＡｓとは格子定数の異なるＧａＰからなるｎ型ＧａＰ層を成長させなければならない。このため、このような条件下におけるＧａＰ層の成長は困難であり、気相成長装置内のサセプタ等の部材に生じる原料ガスの析出のような外乱要因に影響され易い。そしてこれによって、ＧａＰ層の成長速度すなわちＧａＰ層の厚さにバラツキが生じ、その後製造される発光素子の不良の原因となり、歩留まりを落とす大きな原因となることが問題となっていた。 However, in such a method, an n-type GaP layer made of GaP having a lattice constant different from that of GaAs must be grown on a light-emitting layer lattice-matched to GaAs, which is the material of the n-type GaAs substrate. For this reason, it is difficult to grow a GaP layer under such conditions, and it is easily affected by disturbance factors such as deposition of a source gas generated in a member such as a susceptor in a vapor phase growth apparatus. This causes a variation in the growth rate of the GaP layer, that is, the thickness of the GaP layer, which causes a defect in a light emitting device manufactured thereafter, and causes a large decrease in yield.
　このような問題点に鑑みて、本発明者らが鋭意検討した結果、基板上にＩＩＩ－Ｖ族化合物半導体層をハイドライド気相成長法によってエピタキシャル成長させている途中に、少なくとも１回該エピタキシャル成長を中断して気相成長装置内のガスエッチングを行うことにより、サセプタ等の部材に生じる原料ガスの析出を抑制し、ＧａＰ層の厚さのバラツキを低減できることを見出し、本発明を完成させた。 In view of these problems, the present inventors have conducted intensive studies, and as a result, the epitaxial growth was interrupted at least once while the III-V compound semiconductor layer was epitaxially grown on the substrate by hydride vapor phase epitaxy. Then, by performing gas etching in the vapor phase growth apparatus, it was found that the deposition of the source gas generated in a member such as a susceptor can be suppressed and the variation in the thickness of the GaP layer can be reduced, and the present invention has been completed.
　以下に本発明の気相成長方法の実施形態を図面に基づき詳細に説明するが、本発明はこれのみに限定されるものではない。 Hereinafter, embodiments of the vapor phase growth method of the present invention will be described in detail with reference to the drawings, but the present invention is not limited thereto.
　まず、本発明の気相成長方法を適応することができる気相成長装置について、図１を参照しながら簡単に説明する。尚、図１にはバレル型の気相成長装置を示しているが、その他水平型や縦型等の気相成長装置であっても、本発明の気相成長方法を適応させることが可能である。 First, a vapor phase growth apparatus capable of applying the vapor phase growth method of the present invention will be briefly described with reference to FIG. Although FIG. 1 shows a barrel type vapor phase growth apparatus, the vapor phase growth method of the present invention can be applied to other vapor phase growth apparatuses such as a horizontal type and a vertical type. is there.
　気相成長装置１は、チャンバー２の内部に、ＩＩＩ族金属化合物を生成するＩＩＩ族金属化合物生成管３を具備する。このＩＩＩ族金属化合物生成管３は内部に、ＩＩＩ族金属を搭載したリザーバ４を有するものである。また、ＩＩＩ族金属化合物生成管３は第一のヒーター５によって加熱される。複数のＩＩＩ族金属元素を含むＩＩＩ－Ｖ族化合物半導体層を形成する場合にはそれらの金属の混合物の比率を調整してリザーバ４に搭載すればよい。 The vapor phase growth apparatus 1 includes a group III metal compound generation tube 3 for generating a group III metal compound inside the chamber 2. This group III metal compound production tube 3 has a reservoir 4 in which a group III metal is mounted. The group III metal compound production tube 3 is heated by the first heater 5. When forming a group III-V compound semiconductor layer containing a plurality of group III metal elements, the ratio of the mixture of these metals may be adjusted and mounted on the reservoir 4.
　気相成長装置１は、さらに、Ｖ族元素を導入するＶ族元素導入管（不図示）と、基板Ｗを載置する回転自在のサセプタ６と、各種ガスを排出するガス排出管（不図示）と、基板Ｗを加熱する第二のヒーター７等を具備する。 The vapor phase growth apparatus 1 further includes a group V element introduction pipe (not shown) for introducing a group V element, a rotatable susceptor 6 on which the substrate W is placed, and a gas discharge pipe (not shown) for discharging various gases. And a second heater 7 for heating the substrate W.
　このような構造を有する気相成長装置１を用いて、以下のようにＩＩＩ－Ｖ族化合物半導体層のエピタキシャル成長を行う。 Using the vapor phase growth apparatus 1 having such a structure, the III-V compound semiconductor layer is epitaxially grown as follows.
　まず、基板Ｗを準備して気相成長装置１内のサセプタ６上に載置する。この基板Ｗとしては、特には限定されないが、例えばＧａＡｓ、ＧａＮ、ＧａＰ等のＩＩＩ－Ｖ族化合物半導体基板とすることができる。 First, the substrate W is prepared and placed on the susceptor 6 in the vapor phase growth apparatus 1. The substrate W is not particularly limited. For example, a III-V group compound semiconductor substrate such as GaAs, GaN, or GaP can be used.
　その後、基板Ｗ上にハイドライド気相成長法によってＩＩＩ－Ｖ族化合物半導体層をエピタキシャル成長させる。このＩＩＩ－Ｖ族化合物半導体層としては特には限定されないが、例えばＧａＰ層とすることができる。 Thereafter, a III-V compound semiconductor layer is epitaxially grown on the substrate W by hydride vapor phase epitaxy. The III-V group compound semiconductor layer is not particularly limited, but can be, for example, a GaP layer.
　上記ハイドライド気相成長法によるＩＩＩ－Ｖ族化合物半導体層のエピタキシャル成長方法としては、例えばＩＩＩ－Ｖ族化合物半導体層をＧａＰ層とする場合、ＨＶＰＥ装置１内にてＩＩＩ族元素である金属ＧａをＩＩＩ族金属化合物生成管３内のリザーバ４に搭載し、第一のヒーター５によって所定の温度に加熱保持しながら、その金属Ｇａ上に塩化水素を導入することにより、下記（１）式の反応によりＧａＣｌを生成させ、キャリアガスであるＨ２ガスとともに基板Ｗ上に供給する。
 
　Ｇａ（液体）＋ＨＣｌ（気体）　→　ＧａＣｌ（気体）＋１／２Ｈ２（気体）　（１）
  As an epitaxial growth method of the III-V compound semiconductor layer by the hydride vapor phase epitaxy method, for example, when the III-V compound semiconductor layer is a GaP layer, the group III element metal Ga in the HVPE apparatus 1 is III. By mounting hydrogen chloride on the metal Ga while being heated to a predetermined temperature by the first heater 5 while being mounted on the reservoir 4 in the group metal compound production tube 3, the reaction of the following formula (1) GaCl is generated and supplied onto the substrate W together with H 2 gas which is a carrier gas.

Ga (liquid) + HCl (gas) → GaCl (gas) + 1 / 2H 2 (gas) (1)
　エピタキシャル成長温度は例えば６４０℃以上８６０℃以下に設定する。また、Ｖ族元素であるＰは、ＰＨ３（ホスフィン）をキャリアガスであるＨ２とともに基板上に供給する。そして下記（２）の反応によりＧａＰを生成させ、基板上に積層させる。
 
　　ＧａＣｌ（気体）＋ＰＨ３（気体）
　　　　　　→　ＧａＰ（固体）＋ＨＣｌ（気体）＋Ｈ２（気体）　　　　　　（２）
  The epitaxial growth temperature is set to, for example, 640 ° C. or more and 860 ° C. or less. Further, P which is a group V element supplies PH 3 (phosphine) onto the substrate together with H 2 which is a carrier gas. And GaP is produced | generated by reaction of following (2), and is laminated | stacked on a board | substrate.

GaCl (gas) + PH 3 (gas)
→ GaP (solid) + HCl (gas) + H 2 (gas) (2)
　このようにして基板Ｗ上にＩＩＩ－Ｖ族化合物半導体層をエピタキシャル成長させる場合に、原料ガスの全てが基板Ｗ上のエピタキシャル成長に供給されるわけではなく、サセプタ６上等にも堆積が生じる。そこで本発明では、エピタキシャル成長の途中で、少なくとも１回、好ましくは２回以上、より好ましくは５回以上該エピタキシャル成長を中断して気相成長装置１内のガスエッチングを行う。 In this way, when the III-V compound semiconductor layer is epitaxially grown on the substrate W, not all of the source gas is supplied to the epitaxial growth on the substrate W, and deposition also occurs on the susceptor 6 and the like. Therefore, in the present invention, during the epitaxial growth, the epitaxial growth is interrupted at least once, preferably two times or more, more preferably five times or more, and gas etching in the vapor phase growth apparatus 1 is performed.
　ここで、本発明者らが鋭意研究した結果、気相成長装置内のサセプタ等の部材に生じる原料ガスの析出物の数及び大きさは、エピタキシャル成長の後半部において共に著しく増加することを見出した。
　すなわち、ガスエッチングを行うタイミングとしては、特には限定されないが、気相成長装置１内のサセプタ６等の部材に生じた析出物の数が比較的少なく、大きさの比較的小さい段階であるエピタキシャル成長の前半部において行うことが好ましい。またガスエッチングを２回以上行う場合、一度ガスエッチングを行った後に再び生じた析出物の数が比較的少なく、大きさの比較的小さい段階で次のガスエッチングを行うことが好ましい。このようにすれば、より効果的に原料ガスの析出物によるエピタキシャル成長への影響を抑制することができる。 Here, as a result of intensive studies by the present inventors, it has been found that the number and size of source gas precipitates generated on members such as a susceptor in a vapor phase growth apparatus increase remarkably in the latter half of epitaxial growth.
That is, the timing for performing the gas etching is not particularly limited, but the first half of the epitaxial growth, which is a stage in which the number of precipitates generated in the member such as the susceptor 6 in the vapor phase growth apparatus 1 is relatively small and the size is relatively small. It is preferable to carry out in the part. Further, when the gas etching is performed twice or more, it is preferable to perform the next gas etching at a stage where the number of precipitates generated again after performing the gas etching once is relatively small and the size is relatively small. In this way, it is possible to more effectively suppress the influence on the epitaxial growth due to the deposit of the source gas.
　また、ＩＩＩ－Ｖ族化合物半導体層のエピタキシャル成長途中に、気相成長装置１内のガスエッチングを行う方法としては、まずエピタキシャル成長工程として、例えば図１（ａ）に示したようなガス供給条件で原料ガス及びキャリアガスを気相成長装置１内に供給し、上記の方法でＩＩＩ－Ｖ族化合物半導体層を一定時間（例えば１時間）エピタキシャル成長させる。次にガスエッチング工程として、ガス供給条件を例えば図１（ｂ）に示したような条件に切り替えて、エピタキシャル成長工程よりも短い処理時間（例えば３分）で気相成長装置１内のガスエッチングを行う。そしてこれらエピタキシャル成長工程とガスエッチング工程を交互に繰り返すこととすれば、より効率的に気相成長装置１内のサセプタ６等の部材に生じる原料ガスの析出物を除去しながら前記ＩＩＩ－Ｖ族化合物半導体層をエピタキシャル成長させることができるため好ましい。 Further, as a method of performing gas etching in the vapor phase growth apparatus 1 during the epitaxial growth of the III-V group compound semiconductor layer, first, as an epitaxial growth process, for example, a material is supplied under the gas supply conditions as shown in FIG. A gas and a carrier gas are supplied into the vapor phase growth apparatus 1, and the III-V compound semiconductor layer is epitaxially grown for a certain time (for example, 1 hour) by the above method. Next, as the gas etching process, the gas supply conditions are switched to the conditions shown in FIG. 1B, for example, and the gas etching in the vapor phase growth apparatus 1 is performed in a shorter processing time (for example, 3 minutes) than the epitaxial growth process. Do. If the epitaxial growth step and the gas etching step are alternately repeated, the III-V compound can be removed while removing the deposits of the source gas generated on the member such as the susceptor 6 in the vapor phase growth apparatus 1 more efficiently. This is preferable because the semiconductor layer can be epitaxially grown.
　また、前記気相成長装置１内のガスエッチングに用いるエッチングガスとして、ＨＣｌガスを用いれば、一般的なハイドライド気相成長法においては、原料ガスとしてＨＣｌガスを用いるため、前記ＩＩＩ－Ｖ族化合物半導体層のエピタキシャル成長と気相成長装置１内のガスエッチングをより効率的に行うことができるため好ましい。
　特に前述のようにエピタキシャル成長工程とガスエッチング工程を繰り返す方法を用いる場合には、エピタキシャル成長工程からガスエッチング工程へとガス供給条件を切り替える際に、図１（ｂ）のようにＨＣｌガスをＩＩＩ族金属化合物生成管３のリザーバ４に搭載された金属Ｇａに接触させないように流せば良いため、非常に簡便であり効率的である。 Further, when HCl gas is used as an etching gas used for gas etching in the vapor phase growth apparatus 1, the general hydride vapor phase growth method uses HCl gas as a source gas. It is preferable because epitaxial growth of the semiconductor layer and gas etching in the vapor phase growth apparatus 1 can be performed more efficiently.
In particular, when the method of repeating the epitaxial growth process and the gas etching process as described above is used, when the gas supply condition is switched from the epitaxial growth process to the gas etching process, HCl gas is used as a group III metal as shown in FIG. Since it suffices that the metal Ga mounted on the reservoir 4 of the compound generation tube 3 is not brought into contact with the reservoir 4, it is very simple and efficient.
　ここで、以下に本発明の発光素子用基板の製造方法の実施形態を、図４に示したフロー図に基づき詳細に説明するが、本発明はこれに限定されるものではない。 Here, an embodiment of the method for manufacturing a substrate for a light-emitting element of the present invention will be described in detail below based on the flowchart shown in FIG. 4, but the present invention is not limited to this.
　まず工程１に示すように、成長用基板としてｎ型ＧａＡｓ基板１１０を準備し、洗浄した後、ＭＯＶＰＥリアクターに入れ、前記ｎ型ＧａＡｓ基板１１０上にｎ型ＧａＡｓバッファ層１２０を０．１～１．０μｍエピタキシャル成長させる。 First, as shown in step 1, an n-type GaAs substrate 110 is prepared as a growth substrate, cleaned, and then placed in a MOVPE reactor, and an n-type GaAs buffer layer 120 is formed on the n-type GaAs substrate 110 by 0.1 to 1 Epitaxial growth is performed.
　次に工程２に示すように前記ｎ型ＧａＡｓバッファ層１２０上に、発光層１３０として各々（ＡｌｘＧａ１－ｘ）ｙＩｎ１－ｙＰ（ただし、０≦ｘ≦１，０≦ｙ≦１）からなる、厚さ０．８～４．０μｍのｎ型クラッド層１３１、厚さ０．４～２．０μｍの活性層１３２及び厚さ０．８～４．０μｍのｐ型クラッド層１３３を、この順序にてエピタキシャル成長させる。 Next, as shown in Step 2, (Al x Ga 1-x ) y In 1-y P (where 0 ≦ x ≦ 1, 0 ≦ y ≦) is formed on the n-type GaAs buffer layer 120 as the light emitting layer 130. 1), an n-type cladding layer 131 having a thickness of 0.8 to 4.0 μm, an active layer 132 having a thickness of 0.4 to 2.0 μm, and a p-type cladding layer 133 having a thickness of 0.8 to 4.0 μm. Are epitaxially grown in this order.
　尚、上記各層のエピタキシャル成長は、公知のＭＯＶＰＥ法により行なわれる。Ａｌ、Ｇａ、Ｉｎ、Ｐの各成分源となる原料ガスとしては、これらに限定されるわけではないが、例えば以下のようなものを使用できる。
・Ａｌ源ガス：トリメチルアルミニウム（ＴＭＡｌ）、トリエチルアルミニウム（ＴＥＡｌ）など。
・Ｇａ源ガス：トリメチルガリウム（ＴＭＧａ）、トリエチルガリウム（ＴＥＧａ）など。
・Ｉｎ源ガス：トリメチルインジウム（ＴＭＩｎ）、トリエチルインジウム（ＴＥＩｎ）など。
・Ｐ源ガス：トリメチルリン（ＴＭＰ）、トリエチルリン（ＴＥＰ）、ホスフィン（ＰＨ３）など。
　また、ドーパントガスとしては、以下のようなものを使用できる。
（ｐ型ドーパント）
・Ｍｇ源：ビスシクロペンタジエニルマグネシウム（Ｃｐ２Ｍｇ）など。
・Ｚｎ源：ジメチル亜鉛（ＤＭＺｎ）、ジエチル亜鉛（ＤＥＺｎ）など。
（ｎ型ドーパント）
・Ｓｉ源：モノシランなどのシリコン水素化物など。 The epitaxial growth of each layer is performed by a known MOVPE method. Although not limited to these as source gas used as each component source of Al, Ga, In, and P, for example, the following can be used.
Al source gas: trimethylaluminum (TMAl), triethylaluminum (TEAl), etc.
Ga source gas: trimethylgallium (TMGa), triethylgallium (TEGa), etc.
In source gas: trimethylindium (TMIn), triethylindium (TEIn), etc.
P source gas: trimethyl phosphorus (TMP), triethyl phosphorus (TEP), phosphine (PH 3 ), etc.
Moreover, the following can be used as dopant gas.
(P-type dopant)
Mg source: biscyclopentadienyl magnesium (Cp 2 Mg), etc.
Zn source: dimethyl zinc (DMZn), diethyl zinc (DEZn), etc.
(N-type dopant)
Si source: silicon hydride such as monosilane.
　次に工程３に進み、ｐ型クラッド層１３３上に厚さ０．０５～２．０μｍのＧａＰ接続層１４０をＭＯＶＰＥ法により成長させ、更にその上に、第一の電流拡散層である厚さ５μｍ～２００μｍのｐ型ＧａＰ層１５０を、ＨＶＰＥ法でエピタキシャル成長する。このＨＶＰＥ法による第一電流拡散層のエピタキシャル成長においても、途中でガスエッチングを行う本発明の気相成長方法を適用することができる。 Next, the process proceeds to Step 3, where a GaP connection layer 140 having a thickness of 0.05 to 2.0 μm is grown on the p-type cladding layer 133 by the MOVPE method, and further, a thickness serving as a first current diffusion layer is formed thereon. A p-type GaP layer 150 of 5 μm to 200 μm is epitaxially grown by HVPE. Also in the epitaxial growth of the first current diffusion layer by the HVPE method, the vapor phase growth method of the present invention in which gas etching is performed in the middle can be applied.
　次に、工程４に示すようにエッチング等によりｎ型ＧａＡｓ基板１１０及びｎ型ＧａＡｓバッファ層１２０を除去する。そして工程５に示すように、ｎ型ＧａＡｓ基板除去によって露出したｎ型クラッド層１３１上に、第二の電流拡散層であるｎ型ＧａＰ層１６０をＨＶＰＥ法でエピタキシャル成長させ、発光素子用基板１００を製造する。 Next, as shown in Step 4, the n-type GaAs substrate 110 and the n-type GaAs buffer layer 120 are removed by etching or the like. Then, as shown in step 5, the n-type GaP layer 160, which is the second current diffusion layer, is epitaxially grown on the n-type cladding layer 131 exposed by the removal of the n-type GaAs substrate by the HVPE method. To manufacture.
　ここで、工程５において、本発明の気相成長法を用いることによって、ｎ型ＧａＰ層１６０のエピタキシャル成長途中に、少なくとも１回、好ましくは２回以上、より好ましくは５回以上エピタキシャル成長を中断して気相成長装置内のガスエッチングを行いながらｎ型ＧａＰ層１６０をエピタキシャル成長させる。 Here, in Step 5, by using the vapor phase growth method of the present invention, the epitaxial growth is interrupted at least once, preferably twice or more, more preferably five times or more during the epitaxial growth of the n-type GaP layer 160. The n-type GaP layer 160 is epitaxially grown while performing gas etching in the vapor phase growth apparatus.
　これにより、ｎ型ＧａＡｓ基板１１０のＧａＡｓによって格子整合された発光層１３０のｎ型クラッド層１３１上に、ＧａＡｓと格子定数の異なるＧａＰからなるｎ型ＧａＰ層１６０を積層しても、前記気相成長装置内のガスエッチングによってサセプタ等の部材に生じる原料ガスの析出物が除去されているため、このような析出物による影響を受けにくい。これによって、バッチ間における前記ｎ型ＧａＰ層の成長速度を均一にすることができ、従ってバッチ間における前記ｎ型ＧａＰ層の厚さのバラツキを確実に低減し、歩留まりを落とすことなく高品質な発光素子用基板を製造することができる。 Thus, even if the n-type GaP layer 160 made of GaP having a lattice constant different from that of GaAs is laminated on the n-type cladding layer 131 of the light emitting layer 130 lattice-matched by GaAs of the n-type GaAs substrate 110, the gas phase Since the deposits of the source gas generated in the susceptor and other members are removed by gas etching in the growth apparatus, they are not easily affected by such deposits. As a result, the growth rate of the n-type GaP layer between batches can be made uniform, and thus the variation in the thickness of the n-type GaP layer between batches can be reliably reduced, and high quality can be achieved without reducing the yield. A substrate for a light emitting element can be manufactured.
　以下、実施例及び比較例を示して本発明をより具体的に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these.
（実施例）
　厚さ２００μｍのｎ型ＧａＡｓ単結晶基板を用意し、該基板上にそれぞれｎ型ＧａＡｓバッファ層を０．５μｍエピタキシャル成長させ、該ｎ型ＧａＡｓバッファ層上に、発光層として（Ａｌ０．８５Ｇａ０．１５）０．４５Ｉｎ０．５５Ｐにからなるｎ型クラッド層（１．０μｍ）、（Ａｌ０．１Ｇａ０．９）０．４５Ｉｎ０．５５Ｐからなる活性層（０．６μｍ）、（Ａｌ０．８５Ｇａ０．１５）０．４５Ｉｎ０．５５Ｐからなるｐ型クラッド層（１．０μｍ）をＭＯＶＰＥ法によってこの順序で積層した。そして該ｐ型クラッド層上に、第一の電流拡散層であるｐ型ＧａＰ層を成長させた。このｐ型ＧａＰ層は、発光層側にＭＯＶＰＥ法により厚さ２．０μｍのｐ型ＧａＰ接続層を形成した後に、ＨＶＰＥ法により厚さ１００μｍで形成した。 (Example)
An n-type GaAs single crystal substrate having a thickness of 200 μm is prepared, an n-type GaAs buffer layer is epitaxially grown on each of the substrates by 0.5 μm, and a light emitting layer (Al 0.85 Ga 0 is formed on the n-type GaAs buffer layer. .15 ) 0.45 In 0.55 P n-type cladding layer (1.0 μm), (Al 0.1 Ga 0.9 ) 0.45 In 0.55 P active layer (0.6 μm) ), P-type cladding layer (1.0 μm) made of (Al 0.85 Ga 0.15 ) 0.45 In 0.55 P was laminated in this order by the MOVPE method. Then, a p-type GaP layer as a first current diffusion layer was grown on the p-type cladding layer. The p-type GaP layer was formed to a thickness of 100 μm by the HVPE method after forming a 2.0 μm-thick p-type GaP connection layer on the light emitting layer side by the MOVPE method.
　次に前記ｎ型ＧａＡｓ単結晶基板を湿式エッチングにより除去して、前記発光層の、前記ｎ型ＧａＡｓ単結晶基板が除去された側の表面に、第二の電流拡散層であるｎ型ＧａＰ層を次の条件でハイドライド気相成長法によりエピタキシャル成長させ、発光素子用基板を製造した。
＜条件＞
　図１（ａ）に示したようなガス流量で、１時間エピタキシャル成長を行った後、図１（ｂ）に示したようなガス条件に切り替えてＨＣｌガスによって３分間気相成長装置内のガスエッチングを行い、このサイクルを５回繰り返して（エピタキシャル成長１ｈｒ×５回、エッチング４回）、厚さ１５０μｍを目標として前記ｎ型ＧａＰ層のエピタキシャル成長を行った。 Next, the n-type GaAs single crystal substrate is removed by wet etching, and an n-type GaP layer as a second current diffusion layer is formed on the surface of the light emitting layer on the side where the n-type GaAs single crystal substrate is removed. Was epitaxially grown by hydride vapor phase growth under the following conditions to produce a substrate for a light emitting device.
<Conditions>
After epitaxial growth is performed for 1 hour at a gas flow rate as shown in FIG. 1A, the gas conditions shown in FIG. 1B are changed to the gas conditions shown in FIG. This cycle was repeated 5 times (epitaxial growth 1 hr × 5 times, etching 4 times), and the n-type GaP layer was epitaxially grown with a target thickness of 150 μm.
　このような発光素子用基板の製造を５回（５バッチ）行った。本実施例の１バッチの枚数は１０枚とした。各バッチにおいて製造した１０枚の発光素子用基板におけるｎ型ＧａＰ層の厚さの平均値を計測した結果、以下のようになった。
　　１回目：　１５３μｍ
　　２回目：　１５１μｍ
　　３回目：　１５４μｍ
　　４回目：　１５１μｍ
　　５回目：　１５２μｍ Such a light emitting element substrate was manufactured five times (5 batches). The number of batches in this example was 10. As a result of measuring the average value of the thickness of the n-type GaP layer in the 10 light emitting element substrates manufactured in each batch, it was as follows.
1st time: 153μm
Second time: 151μm
3rd: 154μm
4th time: 151μm
5th: 152μm
　このとき、図３（ａ）に示したように、ｎ型ＧａＰ層のエピタキシャル成長を開始してから４時間経過した後であっても、各バッチにおいてサセプタ上に析出したＧａＰの数はいずれも数個であり、大きさは比較的小さいものであった。また、各バッチにおいて製造した発光素子用基板におけるｎ型ＧａＰ層の厚さの平均値の最大値と最小値との差Ｒは、Ｒ＝３μｍであり、バッチ間におけるｎ型ＧａＰ層の厚さのバラツキが後述する比較例に比べて劇的に良くなっていることが分かる。 At this time, as shown in FIG. 3A, the number of GaP deposited on the susceptor in each batch is a number even after 4 hours have passed since the epitaxial growth of the n-type GaP layer was started. The size was relatively small. Moreover, the difference R between the maximum value and the minimum value of the average value of the thickness of the n-type GaP layer in the light emitting element substrate manufactured in each batch is R = 3 μm, and the thickness of the n-type GaP layer between the batches It can be seen that the variation is dramatically improved as compared with the comparative example described later.
（比較例）
　発光層の、ｎ型ＧａＡｓ単結晶基板が除去された側の表面に、第二の電流拡散層であるｎ型ＧａＰ層をエピタキシャル成長させる際に、該エピタキシャル成長途中で気相成長装置内のガスエッチングを行わなかったこと以外は実施例と同様にして発光素子用基板の製造を５回（５バッチ）行った。各バッチの仕込枚数は１０枚とした。このとき、ｎ型ＧａＰ層の厚さは１５０μｍを目標とし、５時間通してエピタキシャル成長を行った。各バッチにおいて製造した発光素子用基板におけるｎ型ＧａＰ層の厚さの平均値を計測した結果、以下のようになった。
　　１回目：　１４６μｍ
　　２回目：　１４９μｍ
　　３回目：　１６８μｍ
　　４回目：　１４１μｍ
　　５回目：　１５８μｍ (Comparative example)
When the n-type GaP layer as the second current diffusion layer is epitaxially grown on the surface of the light emitting layer on the side where the n-type GaAs single crystal substrate is removed, gas etching in the vapor phase growth apparatus is performed during the epitaxial growth. A substrate for a light emitting element was manufactured 5 times (5 batches) in the same manner as in Example except that it was not performed. The number of sheets prepared for each batch was 10. At this time, the thickness of the n-type GaP layer was set to 150 μm, and epitaxial growth was performed for 5 hours. As a result of measuring the average value of the thickness of the n-type GaP layer in the light emitting device substrate manufactured in each batch, it was as follows.
1st time: 146μm
Second time: 149μm
3rd: 168μm
4th time: 141μm
5th: 158μm
　このとき、図３（ｂ）に示したように、ｎ型ＧａＰ層のエピタキシャル成長を開始してから３時間後には各バッチにおいてサセプタ上に析出したＧａＰの数はいずれも１５０～２００個あり、大きさは図３（ｂ）に示したように比較的大きいものばかりであった。また、各バッチにおいて製造した発光素子用基板におけるｎ型ＧａＰ層の厚さの平均値の最大値と最小値との差Ｒは、Ｒ＝２７μｍであり、バッチ間におけるｎ型ＧａＰ層の厚さのバラツキが非常に大きいことが分かる。 At this time, as shown in FIG. 3B, the number of GaP deposited on the susceptor in each batch is 150 to 200 in 3 hours after the epitaxial growth of the n-type GaP layer is started. As shown in FIG. 3B, the size was relatively large. Moreover, the difference R between the maximum value and the minimum value of the average thickness of the n-type GaP layer in the light emitting device substrate manufactured in each batch is R = 27 μm, and the thickness of the n-type GaP layer between batches It can be seen that the variation of is very large.
　以上のことから、気相成長装置内で基板上にＩＩＩ－Ｖ族化合物半導体層をハイドライド気相成長法によってエピタキシャル成長させる際に、エピタキシャル成長途中に、少なくとも１回該エピタキシャル成長を中断して気相成長装置内のガスエッチングを行うことにより、気相成長装置内のサセプタ等の部材における析出物によるエピタキシャル成長への影響を抑制した状態でＩＩＩ－Ｖ族化合物半導体層のエピタキシャル成長を行うことができることがわかる。
　またこれによって、バッチ間における各ＩＩＩ－Ｖ族化合物半導体層の成長速度を均一なものとし、これによってバッチ間における各ＩＩＩ－Ｖ族化合物半導体層の厚さのバラツキを確実に低減できることがわかる。 From the above, when the III-V compound semiconductor layer is epitaxially grown on the substrate in the vapor phase growth apparatus by the hydride vapor phase growth method, the epitaxial growth is interrupted at least once during the epitaxial growth. It can be seen that by performing the gas etching inside, the group III-V compound semiconductor layer can be epitaxially grown in a state where the influence of the precipitates on the member such as the susceptor in the vapor phase growth apparatus on the epitaxial growth is suppressed.
This also shows that the growth rate of each group III-V compound semiconductor layer between batches is made uniform, and this makes it possible to reliably reduce the variation in thickness of each group III-V compound semiconductor layer between batches.
　なお、本発明は上述した実施の形態に限定されるものではない。上述の実施の形態は単なる例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様の効果を奏するものはいかなるものであっても、本発明の技術的範囲に包含されることは無論である。 Note that the present invention is not limited to the embodiment described above. The above-described embodiment is merely an example, and any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and has the same effect can be used. Of course, it is included in the technical scope of the present invention.

Claims (6)

  1. 　気相成長装置内で基板上に、ＩＩＩ－Ｖ族化合物半導体層をハイドライド気相成長法によってエピタキシャル成長させる気相成長方法であって、前記ＩＩＩ－Ｖ族化合物半導体層のエピタキシャル成長途中に、少なくとも１回該エピタキシャル成長を中断して前記気相成長装置内のガスエッチングを行うことを特徴とする気相成長方法。 A vapor phase growth method for epitaxially growing a group III-V compound semiconductor layer on a substrate in a vapor phase growth apparatus by a hydride vapor phase growth method, wherein at least once during the epitaxial growth of the group III-V compound semiconductor layer A vapor phase growth method characterized in that the epitaxial growth is interrupted and gas etching in the vapor phase growth apparatus is performed.
  2. 　前記気相成長装置内のガスエッチングを、前記ＩＩＩ－Ｖ族化合物半導体層のエピタキシャル成長途中に２回以上行うことを特徴とする請求項１に記載の気相成長方法。 2. The vapor phase growth method according to claim 1, wherein the gas etching in the vapor phase growth apparatus is performed twice or more during the epitaxial growth of the group III-V compound semiconductor layer.
  3. 　前記ＩＩＩ－Ｖ族化合物半導体層のエピタキシャル成長途中に、前記気相成長装置内のガスエッチングを行う方法として、前記ＩＩＩ－Ｖ族化合物半導体層をエピタキシャル成長させるエピタキシャル成長工程と、該エピタキシャル成長工程よりも処理時間の短い、前記気相成長装置内のガスエッチング工程と、を交互に繰り返すことを特徴とする請求項２に記載の気相成長方法。 As a method of performing gas etching in the vapor phase growth apparatus during the epitaxial growth of the III-V compound semiconductor layer, an epitaxial growth process for epitaxially growing the III-V compound semiconductor layer, and a processing time longer than that of the epitaxial growth process. 3. The vapor phase growth method according to claim 2, wherein a short gas etching step in the vapor phase growth apparatus is alternately repeated.
  4. 　前記気相成長装置内のガスエッチングを、ＨＣｌガスを用いて行うことを特徴とする請求項１乃至請求項３のいずれか１項に記載の気相成長方法。 4. The vapor phase growth method according to claim 1, wherein the gas etching in the vapor phase growth apparatus is performed using HCl gas. 5.
  5. 　前記ＩＩＩ－Ｖ族化合物半導体層をＧａＰ層とすることを特徴とする請求項１乃至請求項４のいずれか１項に記載の気相成長方法。 The vapor phase growth method according to any one of claims 1 to 4, wherein the III-V compound semiconductor layer is a GaP layer.
  6. 　ｎ型ＧａＡｓ基板上に（ＡｌｘＧａ１－ｘ）ｙＩｎ１－ｙＰ（ただし、０≦ｘ≦１，０≦ｙ≦１）からなるｎ型クラッド層、活性層、ｐ型クラッド層を順次積層することによって発光層を形成する工程と、該発光層上に第一の電流拡散層であるｐ型ＧａＰ層を積層する工程と、前記ｎ型ＧａＡｓ基板をエッチングにより除去する工程と、前記発光層の、前記ｎ型ＧａＡｓ基板が除去された側の表面に第二の電流拡散層であるｎ型ＧａＰ層を積層する工程と、を有する発光素子用基板の製造方法であって、
    　前記ｎ型ＧａＰ層の積層工程において、請求項５に記載の気相成長方法によって、前記発光層の、前記ｎ型ＧａＡｓ基板が除去された側の表面にｎ型ＧａＰ層を積層することを特徴とする発光素子用基板の製造方法。     An n-type cladding layer, an active layer, and a p-type cladding layer made of (Al x Ga 1-x ) y In 1-y P (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 1) are formed on an n-type GaAs substrate. Forming a light emitting layer by sequentially laminating, a step of laminating a p-type GaP layer as a first current diffusion layer on the light emitting layer, a step of removing the n-type GaAs substrate by etching, Laminating an n-type GaP layer, which is a second current diffusion layer, on the surface of the light-emitting layer on the side where the n-type GaAs substrate has been removed, and a method for producing a substrate for a light-emitting element,
    6. In the step of laminating the n-type GaP layer, an n-type GaP layer is laminated on the surface of the light emitting layer on the side where the n-type GaAs substrate is removed by the vapor phase growth method according to claim 5. The manufacturing method of the board | substrate for light emitting elements.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103668446A (en) * 2013-11-25 2014-03-26 东莞市中镓半导体科技有限公司 Controllable precursor passage
CN106238414A (en) * 2016-07-30 2016-12-21 东莞市中镓半导体科技有限公司 A kind of support for cleaning Source

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114335276B (en) * 2022-03-10 2022-05-27 南昌凯捷半导体科技有限公司 940nm reverse polarity infrared LED epitaxial wafer and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002231643A (en) * 2001-02-01 2002-08-16 Sharp Corp Apparatus for manufacturing iii-v compound semiconductor and iii-v compound semiconductor manufacturing method
JP2003517416A (en) * 1999-05-07 2003-05-27 シービーエル テクノロジーズ インコーポレイテッド Continuous hydride vapor phase epitaxy
JP2010027914A (en) * 2008-07-22 2010-02-04 Shin Etsu Handotai Co Ltd Method of fabricating light emitting element and light emitting element
JP2011508428A (en) * 2007-12-20 2011-03-10 エス． オー． アイ． テック シリコン オン インシュレーター テクノロジーズ Method of in-situ chamber cleaning process for mass production of semiconductor materials

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4424497B2 (en) * 2005-02-15 2010-03-03 日立電線株式会社 Method for manufacturing nitride semiconductor crystal

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003517416A (en) * 1999-05-07 2003-05-27 シービーエル テクノロジーズ インコーポレイテッド Continuous hydride vapor phase epitaxy
JP2002231643A (en) * 2001-02-01 2002-08-16 Sharp Corp Apparatus for manufacturing iii-v compound semiconductor and iii-v compound semiconductor manufacturing method
JP2011508428A (en) * 2007-12-20 2011-03-10 エス． オー． アイ． テック シリコン オン インシュレーター テクノロジーズ Method of in-situ chamber cleaning process for mass production of semiconductor materials
JP2010027914A (en) * 2008-07-22 2010-02-04 Shin Etsu Handotai Co Ltd Method of fabricating light emitting element and light emitting element

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103668446A (en) * 2013-11-25 2014-03-26 东莞市中镓半导体科技有限公司 Controllable precursor passage
CN106238414A (en) * 2016-07-30 2016-12-21 东莞市中镓半导体科技有限公司 A kind of support for cleaning Source

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