GALLIUM OXIDE SUBSTRATE

Information

  • Patent Application
  • 20170137965
  • Publication Number
    20170137965
  • Date Filed
    July 01, 2015
    9 years ago
  • Date Published
    May 18, 2017
    7 years ago
Abstract
Provided is a gallium oxide substrate which has less linear pits. Obtained is a gallium oxide substrate wherein the average density of linear pits in a single crystal surface is 1,000 pits/cm2 or less.
Description
TECHNICAL FIELD

The invention relates to a gallium oxide substrate.


BACKGROUND ART

One of crystal growth methods used for producing a gallium oxide single crystal is the EFG (Edge-defined Film-fed Growth) method (see, e.g., PTL 1).


When the gallium oxide single crystal is produced by using the EFG method described in PTL 1, the gallium oxide single crystal is grown from gallium oxide melt.


CITATION LIST
Patent Literature

[PTL 1]


JP-A-2013-237591


SUMMARY OF INVENTION
Technical Problem

In growing the gallium oxide single crystal, oxygen is supplied onto the surface of the gallium oxide melt to prevent the evaporation of the gallium oxide melt during the crystal growth. The present inventors, however, found that if oxygen is excessively supplied onto the surface of the gallium oxide melt, a lot of linear pits are occurred on the surface of the gallium oxide single crystal at the time of processing the grown gallium oxide single crystal into a substrate.


It is an object of an invention to provide a gallium oxide substrate that has a reduced number of linear pits.


Solution to Problem

The above object will be attained by the respective inventions defined by [1] to [3] below.


[1] A gallium oxide substrate, wherein an average value of a density of linear pits is not more than 1000 pits/cm2 in a surface of a single crystal.


[2] The gallium oxide substrate defined by [1], wherein an effective carrier concentration in the single crystal is in a range of 1×1017 [/cm3] to 1×1020 [/cm3].


[3] The gallium oxide substrate defined by [1], wherein an effective carrier concentration in the single crystal is in a range of 2.05×1017 [/cm3] to 2.23×1019 [/cm3].


Advantageous Effects of Invention

According to the invention, a gallium oxide substrate that has a reduced number of linear pits can be provided.





BRIEF DESCRIPTION OF DRAWINGS


FIG. 1 is a cross sectional view showing a main part of an EFG crystal manufacturing apparatus.



FIG. 2 is a perspective view showing a state of a main part during growth of a β-Ga2O3-based single crystal.



FIG. 3 is an optical micrograph showing the surface state of a gallium oxide substrate polished by CMP.



FIG. 4 is an optical micrograph showing the surface state of the gallium oxide substrate etched with phosphoric acid.



FIG. 5 is a graph showing a relation between an effective carrier concentration in the β-Ga2O3-based single crystal and the number of linear pits on the β-Ga2O3-based single crystal per unit area.





DESCRIPTION OF EMBODIMENTS

Preferred embodiments of the invention will be specifically described below in conjunction with the appended drawings.



FIGS. 1 and 2 schematically shows an EFG crystal manufacturing apparatus generally denoted by the reference numeral 10.


The EFG crystal manufacturing apparatus 10 is provided with a crucible 12 containing Ga2O3-based melt 11 obtained by melting Ga2O3-based powder, a die 13 placed in the crucible 12, a lid 14 covering the upper surface of the crucible 12 except an opening 13b of a slit 13a, a seed crystal holder 21 for holding a β-Ga2O3-based seed crystal (hereinafter, referred as “seed crystal”) 20, and a shaft 22 vertically movably supporting the seed crystal holder 21.


The crucible 12 is formed of a heat-resistant metal material such as iridium capable of containing the Ga2O3-based melt 11. The die 13 has the slit 13a to draw up the Ga2O3-based melt 11 by capillary action. The lid 14 prevents the high-temperature Ga2O3-based melt 11 from evaporating from the crucible 12 and also prevents the vapor of the Ga2O3-based melt 11 from attaching to a portion other than the upper surface of the slit 13a.


The seed crystal 20 is moved down and is brought into contact with the Ga2O3-based melt 11 drawn up to the opening 13b through the slit 13a of the die 13 by capillary action, and the seed crystal 20 in contact with the Ga2O3-based melt 11 is pulled up, thereby growing a β-Ga2O3-based single crystal 23 into a plate shape. The crystal orientation of the β-Ga2O3-based single crystal 23 is the same as the crystal orientation of the seed crystal 20. To control the crystal orientation of the β-Ga2O3-based single crystal 23, for example, a plane orientation and an angle in a horizontal plane of the bottom surface of the seed crystal 20 are adjusted.


A surface 24 is a principal surface of the β-Ga2O3-based single crystal 23 which is parallel to a slit direction of the slit 13a. When a β-Ga2O3-based substrate is formed by cutting the grown β-Ga2O3-based single crystal 23, the plane orientation of the surface 24 of the β-Ga2O3-based single crystal 23 is made to coincide with the plane orientation of the principal surface of the β-Ga2O3-based substrate. For example, when forming a β-Ga2O3-based substrate of which principal surface is, e.g., a (−201) plane, the plane orientation of the surface 24 is (−201).


The seed crystal 20 and the β-Ga2O3-based single crystal 23 are β-Ga2O3 single crystals, or β-Ga2O3 single crystals containing an element such as Cu, Ag, Zn, Cd, Al, In, Si, Ge or Sn.


The β-Ga2O3-based single crystal 23 is grown using a mixed gas of oxygen O2 and at least one type of inert gas such as nitrogen N2, argon Ar or helium He. The atmosphere used for growth of the β-Ga2O3-based single crystal 23 is a mixture of nitrogen N2 and oxygen O2 in the present embodiment, but it is not particularly limited thereto.


Since the Ga2O3-based melt 11 evaporates during the growth of the β-Ga2O3-based single crystal 23, it is preferable that a β-Ga2O3 single crystal be formed under the condition of the gas with a required flow ratio of oxygen to the Ga2O3-based melt 11. The upper limit of the flow ratio of oxygen O2 to nitrogen N2 is controlled to not more than 2% in the present embodiment, but it is not particularly limited thereto.


A gallium oxide substrate is cut out from the β-Ga2O3-based single crystal 23 having an average linear pit density of not more than 1000 pits/cm2.


Pits are crystal defects which appear as recesses on a crystal surface. The linear pits mentioned above are linear pits having a length of about several μm to several hundred μm and extending in a [010] direction. The length, width, depth and shape, etc., thereof are not specifically limited but point pits are not regarded as the linear pits.


Based on the findings by the present inventors, the yield of devices can be increased when gallium oxide substrates having an average linear pit density of not more than 1000 pits/cm2 are used to manufacture the devices. Thus, not more than 1000 pits/cm2 of the average linear pit density can be an indicator for proving a high-quality gallium oxide substrate.


A linear pit density of the gallium oxide substrate which is cut out from the β-Ga2O3-based single crystal 23 is evaluated by, e.g., the following method.


To evaluate the linear pit density, a thin plate-shaped gallium oxide substrate is firstly cut out from the β-Ga2O3-based single crystal 23. Next, a principal surface of the thin plate-shaped gallium oxide substrate is polished.



FIG. 3 is an optical micrograph showing the surface state of a gallium oxide substrate polished by CMP (chemical mechanical planarization). FIG. 4 is an optical micrograph showing the surface state of the gallium oxide substrate etched with phosphoric acid. In general, the substrate manufacturing process is completed with CMP. However, in the present embodiment, phosphoric acid etching is also performed for the purpose of evaluation to allow linear pits to be easily observed, and the linear pit density is checked by counting the number of pits per unit area.



FIG. 5 is a graph showing a relation between a difference between a donor concentration ND and an acceptor concentration NA (an effective carrier concentration ND-NA) in the β-Ga2O3-based single crystal 23 per unit cubic centimeter and the number of linear pits on the β-Ga2O3-based single crystal 23 per unit area. The effective carrier concentration was evaluated by C-V measurement. The measurement range of the effective carrier concentration is from 1×1017 to 1×1020 [/cm3].


In FIG. 5, filled diamonds indicate the measured values when the flow ratio of oxygen O2 to nitrogen N2 is 2%, open squares indicate the measured values when the flow ratio of oxygen O2 to nitrogen N2 is 1%, and open triangles indicate the measured values when the flow ratio of oxygen O2 to nitrogen N2 is 0%.


When the flow ratio of oxygen O2 to nitrogen N2 supplied during growth of the β-Ga2O3-based single crystal is reduced from 2% to not more than 1%, the average density of linear pits occurred on the surface of the gallium oxide substrate cut out from the β-Ga2O3-based single crystal 23 can be reduced to not more than 1000 pits/cm2.


When the flow ratio of oxygen O2 to nitrogen N2 is 2%, the average density of linear pits occurred on the surface of the gallium oxide substrate varies depending on the level of the effective carrier concentration ND-NA, as obvious from FIG. 5. On the other hand, when the flow ratio of oxygen O2 to nitrogen N2 is not more than 1%, the linear pits can be reduced to not more than 1000 pits/cm2 regardless of the level of the effective carrier concentration ND-NA.


Based on FIG. 5, a lower limit in the measurement range of the effective carrier concentration ND-NA is 2.05×1017 [/cm3] when the flow ratio of oxygen O2 to nitrogen N2 is 2%.


When the flow ratio of oxygen O2 to nitrogen N2 is 2%, the linear pit density of the β-Ga2O3-based single crystal 23 is zero even if the effective carrier concentration ND-NA is reduced to the range of 2.05×1017 to 5.96×1017 [/cm3], and it is derived therefrom that the linear pit density is zero even at the effective carrier concentration ND-NA of not more than 2.05×1017 [/cm3]. Thus, it is derived that the linear pit density is zero even when the effective carrier concentration is reduced to about 1×1017 [/cm3] which is the lower limit of the evaluation range.


On the other hand, an upper limit in the measurement range of the effective carrier concentration ND-NA is 2.23×1019 [/cm3] when the flow ratio of oxygen O2 to nitrogen N2 is 2%, as shown in FIG. 5.


When the flow ratio of oxygen O2 to nitrogen N2 is 2%, the linear pit density of the β-Ga2O3-based single crystal 23 is zero even if the effective carrier concentration ND-NA is increased to the range of 1.17×1019 to 2.23×1019 [/cm3], and it is derived therefrom that the linear pit density is zero even at the effective carrier concentration ND-NA of not less than 2.23×1019 [/cm3]. Thus, it is derived that the linear pit density is zero even when the effective carrier concentration is increased to about 1×1020 [/cm3] which is the upper limit of the evaluation range.


When the flow ratio of oxygen O2 to nitrogen N2 is 1%, a lower limit in the measurement range of the effective carrier concentration ND-NA is 4.2×1018 [/cm3] and an upper limit in the measurement range of the effective carrier concentration ND-NA is 1.15×1019 [/cm3].


Thus, if the effective carrier concentration ND-NA is in the range of 4.2×1018 to 1.15×1019 [/cm3], the average density of linear pits on the β-Ga2O3-based single crystal 23 can be reduced to not more than 1000 pits/cm2 by controlling the oxygen flow rate to 1%.


When the flow ratio of oxygen O2 to nitrogen N2 is 0%, a lower limit in the measurement range of the effective carrier concentration ND-NA is 1.28×1018 [/cm3] and an upper limit in the measurement range of the effective carrier concentration ND-NA is 1.07×1019 [/cm3].


Thus, if the effective carrier concentration ND-NA is in the range of 1.28×1018 to 1.07×1019 [/cm3], the average density of linear pits on the β-Ga2O3-based single crystal 23 can be reduced to not more than 1000 pits/cm2 by controlling the oxygen flow rate to 0%.


Effects of the Embodiment

In the present embodiment, a gallium oxide substrate having an average linear pit density of not more than 1000 pits/cm2 can be obtained by controlling the amount of oxygen in the atmosphere gas used during growth of the β-Ga2O3-based single crystal 23.


By using such gallium oxide substrate as a growth substrate, it is possible to epitaxially grow a high-quality crystal film with low linear pit density.


As a result, it is possible to increase the yield of LED device or power device, etc., formed using the gallium oxide substrate and a crystal film thereon.


Although the typical embodiment, modification and illustrated example of the invention have been described, the invention according to claims is not intended to be limited to the embodiment, modification and illustrated example, as obvious from the above description. Therefore, it should be noted that all combinations of the features described in the embodiment, modification and illustrated example are not necessary to solve the problem of the invention.


Industrial Applicability

A gallium oxide substrate which has a reduced number of linear pits is provided.


Reference Signs List




  • 10 EFG CRYSTAL MANUFACTURING APPARATUS


  • 11 Ga2O3-BASED MELT


  • 12 CRUCIBLE


  • 13 DIE


  • 13
    a SLIT


  • 13
    b OPENING


  • 14 LID


  • 20 β-Ga2O3-BASED SEED CRYSTAL


  • 21 SEED CRYSTAL HOLDER


  • 22 SHAFT


  • 23 β-Ga2O3-BASED SINGLE CRYSTAL


Claims
  • 1. A gallium oxide substrate, wherein an average value of a density of linear pits is not more than 1000 pits/cm2 in a surface of a single crystal.
  • 2. The gallium oxide substrate according to claim 1, wherein an effective carrier concentration in the single crystal is in a range of 1×1017 [/cm3] to 1×102° [/cm3].
  • 3. The gallium oxide substrate according to claim 1, wherein an effective carrier concentration in the single crystal is in a range of 2.05×1017 [/cm3] to 2.23×1019 [/cm3].
Priority Claims (1)
Number Date Country Kind
2014-137223 Jul 2014 JP national
PCT Information
Filing Document Filing Date Country Kind
PCT/JP2015/069015 7/1/2015 WO 00