WO2017098756A1 - 13族元素窒化物結晶基板および機能素子 - Google Patents
13族元素窒化物結晶基板および機能素子 Download PDFInfo
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- WO2017098756A1 WO2017098756A1 PCT/JP2016/075175 JP2016075175W WO2017098756A1 WO 2017098756 A1 WO2017098756 A1 WO 2017098756A1 JP 2016075175 W JP2016075175 W JP 2016075175W WO 2017098756 A1 WO2017098756 A1 WO 2017098756A1
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- H01L21/02518—Deposited layers
- H01L21/0257—Doping during depositing
- H01L21/02573—Conductivity type
-
- 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
- H01L33/0075—Processes for devices with an active region comprising only III-V compounds comprising nitride compounds
Definitions
- the present invention relates to a group 13 element nitride crystal substrate and a functional element using the same.
- the present invention is, for example, a technical field that requires high quality, for example, a high color rendering blue LED, a blue-violet laser for high-speed and high-density optical memory, which is said to be a next-generation light source that replaces a fluorescent lamp, and an inverter for a hybrid vehicle. It can use for the power device etc. which are used for.
- the HVPE method is well known as a method for manufacturing a gallium nitride free-standing substrate. Among these, as a method for obtaining high-quality crystals, a DEEP method (Patent Document 1, Non-Patent Document 1) and a VAS method (Patent Documents 2 and 3) are disclosed.
- the flux method is one of liquid phase methods.
- gallium nitride the temperature required for crystal growth of gallium nitride can be relaxed to about 800 ° C. and the pressure can be reduced to several MPa by using metallic sodium as the flux. .
- nitrogen gas is dissolved in a mixed melt of metallic sodium and metallic gallium, and gallium nitride becomes supersaturated and grows as crystals.
- dislocations are less likely to occur than in a gas phase method, so that high-quality gallium nitride having a low dislocation density can be obtained (Patent Document 4).
- the group 13 element nitride crystal layer has high conductivity. For this reason, the inventor tried to increase the output by improving the conductivity of the crystal layer by doping the crystal layer with a dopant such as Si or oxygen.
- An object of the present invention is to obtain desired conductivity in a group 13 element nitride crystal substrate and to improve the function by effectively using the conductivity of the group 13 element nitride crystal.
- the crystal substrate according to the present invention is: An underlayer having a first main surface and a second main surface, and a thick film made of a group 13 element nitride provided on the first main surface of the underlayer.
- the underlayer includes a low carrier concentration region and a high carrier concentration region extending between the first main surface and the second main surface, and the carrier concentration of the low carrier concentration region is 10 17 / cm 3 or less.
- the defect density in the low carrier concentration region is 10 7 / cm 2 or less
- the carrier concentration in the high carrier concentration region is 10 19 / cm 3 or more
- the defect density in the high carrier concentration region is 10 8 / cm 2.
- the carrier concentration of the thick film is 10 18 / cm 3 or more and 10 19 / cm 3 or less
- the defect density of the thick film is 10 7 / cm 2 or less.
- the present invention includes the functional layer made of the group 13 element nitride formed on the crystal substrate and the crystal substrate.
- the high carrier concentration region is between the front surface and the back surface of the crystal substrate. It was confirmed to extend in a column shape so as to penetrate the substrate. At the same time, it was confirmed that the low carrier concentration region also extended in a columnar shape so as to penetrate the substrate between the front surface and the back surface of the crystal substrate. This means that current concentration tends to occur through the high carrier concentration region.
- the above-mentioned phenomenon discovered by the present inventor is a phenomenon different from the efficiency droop phenomenon, but it has never been reported so far and is a newly discovered finding. Based on the above observations, it is the first time this time that current concentration occurs locally.
- the present inventor formed a thick film by re-growing a group 13 element nitride crystal on an underlayer made of group 13 element nitride, and devised the growth conditions at this time, It was found that defect association can be promoted in the film. As a result, it was confirmed that the columnar high carrier concentration region in the crystal substrate was dispersed in the thick film so that the carriers were distributed relatively uniformly, and the CL showed relatively uniform light emission.
- a thick film having such a cross-sectional structure on the underlayer current leakage between a pair of main surfaces of the crystal substrate was successfully suppressed. Thereby, even if the voltage applied to the crystal substrate is increased, current leakage is suppressed, so that the function can be improved by effectively utilizing the conductivity of the crystal substrate.
- FIG. (A) is a schematic diagram which shows the crystal substrate 1 which concerns on embodiment of this invention
- (b) is a schematic diagram which shows the functional element 16 formed by forming the functional element structure 6 on the board
- FIG. (A) shows the state in which the seed crystal film 12 is provided on the support substrate 11,
- (b) shows the state in which the underlayer 13 made of a group 13 element nitride crystal is provided on the seed crystal film 12,
- C) shows a state in which the thick film 14 is provided on the base layer 13.
- (A) is a schematic diagram showing the nucleus 20 generated on the seed crystal 12, and
- (b) is a schematic diagram showing the growth direction from the nucleus 20.
- (A) shows a state in which the underlayer 13 and the thick film 14 are separated from the seed crystal film, and
- (b) shows a crystal substrate 1 obtained by polishing the underlayer 13 and the thick film 14 in (a). Indicates.
- a thick film 3 made of a group 13 element nitride is formed on an underlayer 2 made of a group 13 element nitride.
- the underlayer 2 has a first main surface 2a and a second main surface 2b.
- a thick film 3 is provided on the first main surface 2 a of the underlayer 2.
- the underlayer 2 includes a low carrier concentration region 5 and a high carrier concentration region 4 penetrating between the first main surface 2a and the second main surface 2b. It was confirmed that each of the regions 4 and 5 was generated through the base layer 2 between the first main surface and the second main surface.
- the carrier concentration of the low carrier concentration region 5 is 10 17 / cm 3 or less, and the defect density of the low carrier concentration region 5 is 10 7 / cm 2 or less.
- the carrier concentration of the high carrier concentration region 4 is 10 19 / cm 3 or more, and the defect density of the high carrier concentration region 4 is 10 8 / cm 2 or more. From the mechanism described above, the concentration of the dopant in the high carrier concentration region increases the carrier concentration, and also concentrates the defects in the same region and extends so as to penetrate the base layer between the main surfaces of the base layer. I found it.
- the carrier concentration in the low carrier concentration region is preferably 8 ⁇ 10 16 / cm 3 or less.
- the carrier concentration in the low carrier concentration region is often 1 ⁇ 10 17 / cm 3 or less and 1 ⁇ 10 16 / cm 3 or more.
- the defect density in the low carrier concentration region is preferably 8 ⁇ 10 6 / cm 2 or less.
- the defect density in the low carrier concentration region is often 2 ⁇ 10 6 / cm 2 or more.
- the carrier concentration of the high carrier concentration region 4 is 10 19 / cm 3 or more, but preferably 2 ⁇ 10 19 / cm 3 or more. Further, in the underlayer in which the low carrier concentration region as described above exists, the carrier concentration in the high carrier concentration region is often 5 ⁇ 10 19 / cm 3 or less. The defect density in the high carrier concentration region is preferably 5 ⁇ 10 7 / cm 2 or less.
- the carrier concentration of the thick film 3 is 10 18 / cm 3 or more and 10 19 / cm 3 or less, and the defect density of the thick film is 10 7 / cm 2 or less.
- the defect density of the thick film is low, the defect density of the thick film is often 2 ⁇ 10 6 / cm 2 or more because it is provided on the base layer having the above-described configuration.
- dopant concentration carrier concentration.
- carrier concentration carrier concentration
- the high carrier concentration region and the low carrier concentration region are measured and identified as follows.
- a cathodoluminescence measuring device for example, MP series manufactured by Horiba, Ltd.
- the magnification is 50 to 500 times and the image capturing area is 0.1 to 1 mm square.
- the carrier concentration and the defect density are measured according to the method and conditions described in the examples.
- the group 13 element constituting the underlayer and the thick film is a group 13 element according to the periodic table established by IUPAC.
- the group 13 element is specifically gallium, aluminum, indium, thallium, or the like.
- This group 13 element nitride is particularly preferably gallium nitride, aluminum nitride, or gallium aluminum nitride.
- the additive include carbon, low melting point metals (tin, bismuth, silver, gold) and high melting point metals (transition metals such as iron, manganese, titanium, and chromium).
- the thickness T3 of the thick film is preferably 1 ⁇ m or more, more preferably 50 ⁇ m or more, and most preferably 100 ⁇ m or more.
- the thickness of the thick film is preferably 300 ⁇ m or less, and more preferably 200 ⁇ m or less.
- the thickness T2 of the underlayer is preferably 50 ⁇ m or more from the viewpoint of easy handling of the crystal substrate.
- the thickness of the underlayer is preferably 200 ⁇ m or less from the viewpoint of conductivity.
- the total thickness (T2 + T3) of the crystal substrate including the base layer and the thick film is preferably 250 to 450 ⁇ m.
- a functional element can be obtained by forming a predetermined functional layer on the surface of the thick film.
- Such a functional layer may be a single layer or a plurality of layers. As functions, it can be used for white LEDs with high luminance and high color rendering, blue-violet laser disks for high-speed and high-density optical memory, power devices for inverters for hybrid vehicles, and the like.
- the dislocation density inside the LED becomes equal to the thick film of the crystal substrate.
- the film forming temperature of the functional layer is preferably 950 ° C. or higher, and more preferably 1000 ° C. or higher, from the viewpoint of suppressing unnecessary impurities such as carbon. Further, from the viewpoint of suppressing defects, the film formation temperature of the functional layer is preferably 1200 ° C. or lower, and more preferably 1150 ° C. or lower.
- the material of the functional layer is preferably a group 13 element nitride.
- Group 13 elements are Group 13 elements according to the periodic table established by IUPAC.
- the group 13 element is specifically gallium, aluminum, indium, thallium, or the like.
- the light-emitting element structure includes, for example, an n-type semiconductor layer, a light-emitting region provided on the n-type semiconductor layer, and a p-type semiconductor layer provided on the light-emitting region.
- an n-type contact layer 6a, an n-type cladding layer 6b, an active layer 6c, a p-type cladding layer 6d, and a p-type contact layer 6e are formed on the thick film 3 of the crystal substrate. And constitutes the light emitting element structure 6.
- the light emitting element structure can be further provided with an electrode for an n-type semiconductor layer, an electrode for a p-type semiconductor layer, a conductive adhesive layer, a buffer layer, a conductive support, and the like (not shown).
- the translucent electrode is a translucent electrode made of a metal thin film or a transparent conductive film formed on almost the entire surface of the p-type semiconductor layer.
- the material of the semiconductor constituting the n-type semiconductor layer and the p-type semiconductor layer is made of a III-V group compound semiconductor, and examples thereof are as follows.
- Examples of the doping material for imparting n-type conductivity include silicon, germanium, and oxygen.
- magnesium and zinc can be illustrated as a dope material for providing p-type conductivity.
- MOCVD metal organic chemical vapor deposition method
- MBE molecular beam epitaxy method
- HVPE method hydride vapor phase epitaxy method
- the MOCVD method can obtain a semiconductor layer with good crystallinity and flatness.
- alkyl metal compounds such as TMG (trimethyl gallium) and TEG (triethyl gallium) are often used as the Ga source, and gases such as ammonia and hydrazine are used as the nitrogen source.
- the light emitting region includes a quantum well active layer.
- the material of the quantum well active layer is designed so that the band gap is smaller than the materials of the n-type semiconductor layer and the p-type semiconductor layer.
- the quantum well active layer may have a single quantum well (SQW) structure or a multiple quantum well (MQW) structure.
- SQW single quantum well
- MQW multiple quantum well
- the material of a quantum well active layer can illustrate the following.
- An MQW structure in which 10 cycles are formed is mentioned.
- an underlayer and a thick film are sequentially formed on the seed crystal.
- the seed crystal may form a self-supporting substrate (support substrate) by itself, or may be a seed crystal film formed on another support substrate.
- This seed crystal film may be a single layer, or may include a buffer layer on the support substrate side.
- a seed crystal film 12 is formed on the surface 11 a of the support substrate 11.
- the seed crystal film 12 is made of a group 13 element nitride.
- the material of the single crystal constituting the support substrate is not limited, but sapphire, AlN template, GaN template, GaN free-standing substrate, silicon single crystal, SiC single crystal, MgO single Examples thereof include crystals, spinel (MgAl 2 O 4 ), LiAlO 2 , LiGaO 2 , LaAlO 3 , LaGaO 3 , NdGaO 3 and other perovskite complex oxides, SCAM (ScAlMgO 4 ).
- cubic perovskite structure composite oxides (1) and (2) can be used.
- the growth direction of the group 13 element nitride crystal layer may be the normal direction of the c-plane of the wurtzite structure, or may be the normal direction of the a-collision plane and the m-plane.
- the dislocation density on the surface 12a of the seed crystal is desirably low from the viewpoint of reducing the dislocation density of the underlayer provided on the seed crystal.
- the dislocation density on the surface 12a of the seed crystal is preferably 7 ⁇ 10 8 cm ⁇ 2 or less, and more preferably 5 ⁇ 10 8 cm ⁇ 2 or less.
- the lower the dislocation density of the seed crystal the better from the viewpoint of quality, so there is no particular lower limit, but generally it is often 5 ⁇ 10 7 cm ⁇ 2 or more.
- the production method of the seed crystal layer is not particularly limited, but metal organic chemical vapor deposition (MOCVD) method, metal vapor, chemical vapor deposition (HVPE) method, pulsed deposition (PXD) method, MBE method, sublimation method Examples thereof include a vapor phase method such as a liquid phase method such as a flux method.
- MOCVD metal organic chemical vapor deposition
- HVPE chemical vapor deposition
- PXD pulsed deposition
- MBE method sublimation method
- a vapor phase method such as a liquid phase method such as a flux method.
- an underlayer 13 is formed on the seed crystal 12.
- a thick film 14 is formed on the surface 13 a of the base layer 13.
- the underlayer and the thick film are grown by a flux method.
- the type of the flux is not particularly limited as long as the group 13 element nitride can be generated.
- a flux containing at least one of an alkali metal and an alkaline earth metal is used, and a flux containing sodium metal is particularly preferred.
- the raw material of group 13 element is mixed and used.
- a single metal, an alloy, or a compound can be applied, but a single metal of a group 13 element is preferable from the viewpoint of handling.
- the crystal growth is performed using only the concentration gradient as much as possible as the driving force by setting the supersaturation as low as possible and suppressing the convection of the melt. .
- the formation of nuclei is suppressed, and as shown in FIG. 3B, crystals grow from the nuclei 20 upward (arrow C).
- the underlayer is preferably grown by the following method.
- (1A) Increasing the average growth temperature of the melt in the crucible increases the degree of supersaturation and suppresses the formation of nuclei 20 (see FIG. 3A).
- (2A) By holding the upper part of the crucible at a higher temperature than the bottom part of the crucible, the convection of the melt in the crucible is suppressed.
- (3A) Do not stir the melt or reduce the stirring speed.
- the average growth temperature of the melt in the crucible is set to 870 to 885 ° C.
- (2A) Keep the temperature at the top of the crucible 0.5-1 ° C higher than the temperature at the bottom of the crucible.
- (3A) The melt is not stirred or the stirring speed is 30 rpm or less.
- the stirring direction is one direction.
- (4A) The partial pressure of the nitrogen-containing gas is set to 3.5 to 3.8 MPa.
- the crystal defect means threading dislocation.
- threading dislocation There are three types of threading dislocations: screw dislocation (Screw Dislocation), edge dislocation (Edge Dislocation), and mixed dislocation (Mixed Dislocation). These dislocations can be confirmed with a transmission electron microscope (TEM) or cathodoluminescence (CL).
- TEM transmission electron microscope
- CL cathodoluminescence
- the thick film as described above can be formed by re-growing the group 13 element nitride in the same melt by the flux method. That is, the crystal growth rate is increased by changing the growth conditions. As a result, as shown in FIG. 3B, the crystal growth 21 mainly grows in the horizontal direction (arrows A and B).
- the average growth temperature of the melt in the crucible is set to 850 to 860 ° C. Further, the difference in average growth temperature from the initial stage is set to 10 to 25 ° C. (3B) Stir the melt and periodically change the stirring direction. In addition, stop the crucible rotation when changing the direction of rotation. In this case, the rotation stop time is preferably 100 seconds to 6000 seconds, and more preferably 600 seconds to 3600 seconds. The rotation time before and after the rotation stop time is preferably 10 to 600 seconds, and the rotation speed is preferably 10 to 30 rpm. (4B) The partial pressure of the nitrogen-containing gas is set to 4.0 to 4.2 MPa. In addition, the pressure is 0.2 to 0.5 MPa higher than the partial pressure of the nitrogen-containing gas in the initial stage.
- the low dislocation region and the carrier concentration are balanced by gradually changing the manufacturing conditions. Specifically, the stirring speed of the melt is gradually increased, or the holding time at the maximum rotation speed during stirring is gradually increased.
- single crystals are grown in an atmosphere containing a gas containing nitrogen atoms.
- This gas is preferably nitrogen gas, but may be ammonia.
- the gas other than the gas containing nitrogen atoms in the atmosphere is not limited, but an inert gas is preferable, and argon, helium, and neon are particularly preferable.
- the underlayer In the stage of growing the underlayer, it is preferably held for 1 hour or longer, more preferably 2 hours or longer under the conditions (1A) to (4A) described above.
- the holding time at the stage of growing the underlayer is preferably 10 hours or less.
- the ratio (mol ratio) of group 13 element nitride / flux (for example, sodium) in the melt is preferably increased, preferably 18 mol% or more, and more preferably 25 mol% or more.
- this ratio becomes too large, the crystal quality tends to deteriorate, so 40 mol% or less is preferable.
- the hydrogen mixing ratio is increased (for example, 50% or more) and the growth rate is decreased (for example, 10 to 20 microns / hr).
- the state shown in (b) in FIG. 3B is preferentially grown in the direction of arrow C, and then the hydrogen mixing ratio is lowered (for example, 30% or less) and the V / III ratio is increased (for example, 2000 or more).
- a preferential growth in the A and B directions is assumed.
- the group 13 element nitride grown by the flux method emits fluorescence (blue fluorescence) having a peak at a wavelength of 440 to 470 nm when irradiated with light having a wavelength of 330 to 385 nm (for example, light from a mercury lamp).
- the group 13 element nitride produced by the vapor phase method emits fluorescence having a peak at a wavelength of 540 to 580 nm (yellow fluorescence) when irradiated with light having a wavelength of 330 to 385 nm.
- a predetermined functional layer can be formed on the surface 14a of the thick film 14 after forming the crystal substrate 1A on the seed crystal.
- the crystal substrate 1A can be obtained as shown in FIG. 4A by removing the crystal substrate 1A from the seed crystal 12 by grinding, a lift-off method, or the like.
- a predetermined functional layer is provided on the thick film 14 of the separated crystal substrate 1A. At this time, the warping of the crystal substrate can be reduced by polishing the bottom surface 13b of the underlayer 13.
- the surface 3a of the thick film 3 can be made a polished surface as shown in FIG.
- the bottom surface 13b of the underlayer 13 the bottom surface 2a of the underlayer 2 can be used as a polished surface as shown in FIG. 4B.
- the group 13 element nitride crystal layer is disk-shaped, but other forms such as a square plate may be used.
- the crystal layer has a diameter of 25 mm or more. Thereby, an easy-to-handle crystal layer suitable for mass production of functional elements can be provided.
- grinding refers to scraping off the surface of an object by bringing fixed abrasive grains, in which the abrasive grains are fixed with bonds, into contact with the object while rotating at high speed. A rough surface is formed by this grinding.
- a gallium nitride substrate it is formed of high hardness SiC, Al 2 O 3 , diamond, CBN (cubic boron nitride, the same shall apply hereinafter), etc., and contains abrasive grains having a particle size of about 10 ⁇ m to 100 ⁇ m Fixed abrasives are preferably used.
- polishing means that a surface plate and an object are brought into contact with each other through loose abrasive grains (referred to as non-fixed abrasive grains hereinafter), or fixed abrasive grains and Polishing the surface of an object by bringing the object into contact with each other while rotating.
- a surface having a surface roughness smaller than that in the case of grinding and a surface rougher than that in the case of fine polishing (polishing) is formed.
- Abrasive grains formed of SiC, Al 2 O 3 , diamond, CBN, or the like having high hardness and having a particle size of about 0.5 ⁇ m to 15 ⁇ m are preferably used.
- Fine polishing means that a polishing pad and an object are brought into contact with each other through rotating abrasive grains, or a fixed abrasive grain and an object are brought into contact with each other while rotating with respect to each other. This means to smooth and smooth the surface. By such fine polishing, a crystal growth surface having a smaller surface roughness than that in the case of polishing is formed.
- Example 1 A crystal substrate and a light emitting device were manufactured according to the procedure described with reference to FIGS.
- a MOCVD method is used to deposit a low-temperature GaN buffer layer of 20 nm at a temperature of 530 ° C. on a c-plane sapphire substrate 11 having a diameter of 2 inches and a thickness of 500 ⁇ m, and then a GaN film having a thickness of 2 ⁇ m at 1050 ° C.
- a seed crystal film 12 made of The defect density by TEM observation was 1 ⁇ 10 9 / cm 2 .
- the substrate was subjected to ultrasonic cleaning with an organic solvent and ultrapure water for 10 minutes and then dried to obtain a seed crystal substrate.
- the heater installed in the pressure vessel was heated to melt the raw material in the crucible, thereby producing a Ga—Na mixed melt.
- nitrogen gas was introduced from the nitrogen gas cylinder until the pressure became 4.0 MPa, and crystal growth was started.
- the temperature of the crucible was lowered to 850 ° C. over 20 minutes, and the pressure was changed to 4.2 MPa.
- stirring by continuous inversion of the turntable was started to change the crystal growth mode. Thereafter, the pressure was changed to 4.0 MPa over 30 minutes, and stirring by continuous inversion of the turntable was continued to grow crystals.
- the thickness of the GaN crystal increased by approximately 300 microns.
- the surface of the obtained gallium nitride crystal plate was polished to a thickness of 250 microns.
- the dark spot density on the surface was measured by the cathodoluminescence method, it was 2 ⁇ 10 5 / cm 2 . This dark spot density is defined as the defect density.
- a sample cut from the crystal plate into a 6 mm square was measured for the carrier concentration by hole measurement, and found to be 5 ⁇ 10 18 / cm 3 .
- n-GaN was further grown to 100 microns using the liquid phase method.
- the n-type dopant was doped so that the carrier concentration was 1 ⁇ 10 18 / cm 3 .
- the growth condition at this time is that the above-mentioned rotation speed is slowly increased from 20 rpm to 40 rpm over 4 hours, and then the holding time at 35 rpm is increased from 200 seconds to 600 seconds over 4 hours in steps of 100 seconds. I let you. Then, it cooled to room temperature and collect
- the substrate was laser lifted off to separate the support substrate and the seed crystal film from the gallium nitride crystal substrate. Both sides of the crystal substrate were flattened by machining and dry etching to produce a 2-inch wafer 1 having a thickness of 290 microns.
- the thickness of the thick film 3 after polishing was about 40 microns, and the thickness of the underlayer 2 was 250 microns.
- the cross-sectional structure of this wafer was observed by CL. As a result, it was found that the underlayer 2 was divided into a bright region 4 and a dark region 5, both of which grew in a columnar shape when viewed in cross section. In addition, a dark line due to the dislocation concentrated portion was confirmed at the center of the region 4 that emits bright light.
- the defect density of the brightly emitting region 4 was 2 to 5 ⁇ 10 8 / cm 2 , and the carrier concentration was 1 ⁇ 10 19 / cm 3 .
- the defect density in the region 5 where the emission intensity was weak was substantially uniform, 3 ⁇ 10 6 / cm 2 , and the carrier concentration was 8 ⁇ 10 16 / cm 3 .
- the defect density was generally uniform, 3 ⁇ 10 6 / cm 2 , and the carrier concentration was 1 ⁇ 10 18 / cm 3 .
- the carrier concentration was measured using four samples (1 ⁇ 10 17 / cm 3 , 1 ⁇ 10 18 / cm 3 , 5 ⁇ 10 18 / cm 3 , 1 ⁇ 10 19) that were previously determined by an eddy current method.
- CL measurement was performed using 4 types of / cm 3 , and the image brightness was subjected to image processing with 8 bits (255 gradations), and a calibration curve was created for the relationship between the carrier density and the brightness of the CL image.
- the carrier concentration was calculated using a calibration curve.
- Example 1 A crystal substrate was produced in the same manner as in Example 1, and an LED structure was produced thereon. However, unlike Example 1, crystal growth was stopped at the stage of forming the underlayer, and no thick film was formed.
- Example 1 When a cross-sectional observation of the underlayer was performed in the same manner as in Example 1, the bright region 4 and the dark region 5 each extended in a columnar shape along the growth direction and did not intersect. In the brightly emitting region 4, many black lines, which seem to be dislocation lines, were observed. On the other hand, dislocation lines were only sparsely observed in the dark region 5. In addition, the defect density and carrier concentration in each of the regions 4 and 5 were almost the same as those in Example 1.
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Abstract
Description
13族元素窒化物結晶からなり、第一の主面および第二の主面を有する下地層、および
下地層の前記第一の主面上に設けられた13族元素窒化物からなる厚膜を備えており、
下地層が、第一の主面と前記第二の主面との間に延びる低キャリア濃度領域と高キャリア濃度領域とを含んでおり、低キャリア濃度領域のキャリア濃度が1017/cm3以下であり、低キャリア濃度領域の欠陥密度が107/cm2以下であり、高キャリア濃度領域のキャリア濃度が1019/cm3以上であり、高キャリア濃度領域の欠陥密度が108/cm2以上であり、厚膜のキャリア濃度が1018/cm3以上、1019/cm3以下であり、厚膜の欠陥密度が107/cm2以下であることを特徴とする。
(結晶基板)
好適な実施形態においては、図1(a)に示すように、13族元素窒化物からなる下地層2上に、13族元素窒化物からなる厚膜3が形成されている。下地層2は、第一の主面2aおよび第二の主面2bを有する。下地層2の第一の主面2a上に厚膜3が設けられている。
カソードルミネッセンス測定器(たとえば、 (株)堀場製作所製MPシリーズ)を用い、倍率50~500倍、画像撮影領域を0.1~1mm角とする。
キャリア濃度および欠陥密度は、実施例記載の方法および条件にしたがって測定するものとする。
厚膜の表面上に所定の機能層を形成することで、機能素子を得ることができる。
AlyInxGa1-x-yN(0≦x≦1、0≦y≦1)
n型導電性を付与するためのドープ材としては、珪素、ゲルマニウム、酸素を例示できる。また、p型導電性を付与するためのドープ材としては、マグネシウム、亜鉛を例示できる。
好適な実施形態においては、種結晶上に下地層、厚膜を順次形成する。種結晶は、それ自体で自立基板(支持基板)を形成していてよく、あるいは別の支持基板上に形成された種結晶膜であってよい。この種結晶膜は、一層であってよく、あるいは支持基板側にバッファ層を含んでいて良い。
好適な実施形態においては、下地層および厚膜をフラックス法によって育成する。この際、フラックスの種類は、13族元素窒化物を生成可能である限り、特に限定されない。好適な実施形態においては、アルカリ金属とアルカリ土類金属の少なくとも一方を含むフラックスを使用し、ナトリウム金属を含むフラックスが特に好ましい。
(1A) ルツボ内の融液の平均育成温度を高めにすることで過飽和度を大きくして核20の形成を抑制する(図3(a)参照)。
(2A) ルツボの上部をルツボの底部よりも高温に保持することによって、ルツボ内での融液の対流を抑制する。
(3A) 融液の攪拌はしないようにするか、あるいは攪拌速度を小さくする。
(4A) 窒素含有ガスの分圧を低くする。
(1A) ルツボ内の融液の平均育成温度を870~885℃とする。
(2A) ルツボの上部の温度を,ルツボの底部の温度よりも0.5~1℃高く保持する。
(3A) 融液の攪拌はしないようにするか、あるいは攪拌速度を30rpm以下とする。また、攪拌方向を1方向とする。
(4A) 窒素含有ガスの分圧を3.5~3.8MPaとする。
すなわち、育成条件を変更することによって、結晶成長速度を上げる。この結果、図3(b)に示すように、結晶成長21は横方向への成長が主となる(矢印A、B)。
(1B) ルツボ内の融液の平均育成温度を850~860℃とする。また、初期段階との平均育成温度の差を10~25℃とする。
(3B) 融液の攪拌をし、攪拌方向を定期的に変更する。更に、回転方向を変えるときに、ルツボの回転を停止させること。この場合には、回転停止時間は100秒~6000秒が好ましく、600秒~3600秒が更に好ましい。また、回転停止時間の前後における回転時間は10秒~600秒が好ましく、回転速度は10~30rpmが好ましい。
(4B) 窒素含有ガスの分圧を4.0~4.2MPaとする。また、初期段階における窒素含有ガスの分圧よりも0.2~0.5MPa高くする。
例えばHVPE法の場合には、成長初期段階において、水素混合比を高く(例えば50%以上)し、成長速度を遅く(例えば、10~20ミクロン/hr)して図3(a)から図3(b)の矢印C方向に優先成長する状態とし、その後、水素混合比を下げ(例えば30%以下)、V/III比を高くする(例えば2000以上)ことで、図3(b)の矢印A、B方向に優先成長する状態とする。
図2(b)(c)に示すように、種結晶上に結晶基板1Aを形成した後、厚膜14の表面14a上に所定の機能層を形成することができる。あるいは、結晶基板1Aを種結晶12から、研削加工、リフトオフ法等によって除去することによって、図4(a)に示すように結晶基板1Aを得ることができる。この場合には、分離された結晶基板1Aの厚膜14上に所定の機能層を設ける。この際、下地層13の底面13bに研磨加工を施すことで、結晶基板の反りを低減することができる。
研削(グラインディング:grinding)とは、砥粒をボンドで固定した固定砥粒を高速回転させながら対象物に接触させて、対象物の面を削り取ることをいう。かかる研削によって、粗い面が形成される。窒化ガリウム基板の底面を研削する場合、硬度の高いSiC、Al2O3、ダイヤモンドおよびCBN(キュービックボロンナイトライド、以下同じ)などで形成され、粒径が10μm以上100μm以下程度の砥粒を含む固定砥粒が好ましく用いられる。
図1~図4を参照しつつ説明した手順に従い、結晶基板および発光素子を作製した。
MOCVD法を用いて、直径2インチ、厚さ500μmのc面サファイア基板11の上に、530℃にて、低温GaNバッファ層を20nm堆積させたのちに、1050℃にて、厚さ2μmのGaNからなる種結晶膜12を積層させた。TEM観察による欠陥密度は、1×109/cm2であった。有機溶剤、超純水でそれぞれ10分間超音波洗浄した後に乾燥させて、これを種結晶基板とした。
不活性ガスを充填したグローブボックス中で、金属Gaと金属Naをモル比20:80で秤量し、種結晶基板とともに、アルミナ製の坩堝の底に配置した。さらにドーパントとして、液体のゲルマニウム原料をGaに対して1mol/cm3の量を添加した。この坩堝を3段積み重ねて、ステンレス製の保持容器(内々容器)に収納し、さらにこの坩堝が複数段収納された内々容器を4段積み重ねて、ステンレス製の保持容器(内容器)に収納した。
次いで、液相法を用いて、さらにn-GaNを100ミクロン成長させた。キャリア濃度は、1×1018/cm3となるようにn型ドーパントをドープした。
このときの育成条件は、前述の回転速度を20rpmから40rpmまで4時間掛けてゆっくりと増加させ、その後は35rpmでの保持時間を200秒から600秒まで4時間掛けて100秒ずつ段階的に増加させた。その後、室温まで冷却して結晶を回収した。合計8時間で、約100ミクロンの結晶が成長した。
その後、基板をレーザーリフトオフ加工して支持基板および種結晶膜を窒化ガリウム結晶基板から分離した。結晶基板の両面を機械加工およびドライエッチングにて平坦加工を施し、厚さ290ミクロンの2インチウエハー1を作製した。研磨後の厚膜3の厚さは約40ミクロン、下地層2の厚さは250ミクロンであった。
また、得られた厚膜3に対して、波長330~385nmの光を水銀ランプから照射すると、440~470nmにピークを有するブロードな蛍光(青色の蛍光)を発した。
得られた結晶基板を用いて、MOCVD法により、LED構造を作製し、その後電極パターニング、裏面バックポリッシュした。バックポリッシュ後の下地層の厚さは70ミクロンとした。その後ダイシングにより、1mm角の縦型構造の青色LEDを作成した。350mA駆動時における内部量子効率を測定したところ、約80%と高い値が得られた。発光強度は面内で均一であった。さらに駆動電流を1000mAまで増加させてその内部量子効率を測定したところ、65%と高い値を維持していた。また、2V印加時におけるリーク電流は0.01μAと小さかった。
実施例1と同様にして結晶基板を作製し、その上にLED構造を作製した。ただし、実施例1と異なり、下地層を形成する段階で結晶育成を停止し、厚膜を形成しなかった。
以上の実験結果から、下地層の明るく発光する領域4における欠陥集中部がリーク電流の原因となっていることがわかる。
Claims (9)
- 13族元素窒化物結晶からなり、第一の主面および第二の主面を有する下地層、および
前記下地層の前記第一の主面上に設けられた13族元素窒化物結晶からなる厚膜を備える結晶基板であって、
前記下地層が、前記第一の主面と前記第二の主面との間に延びる低キャリア濃度領域と高キャリア濃度領域とを含んでおり、前記低キャリア濃度領域のキャリア濃度が1017/cm3以下であり、前記低キャリア濃度領域の欠陥密度が107/cm2以下であり、前記高キャリア濃度領域のキャリア濃度が1019/cm3以上であり、前記高キャリア濃度領域の欠陥密度が108/cm2以上であり、前記厚膜のキャリア濃度が1018/cm3以上、1019/cm3以下であり、前記厚膜の欠陥密度が107/cm2以下であることを特徴とする、13族元素窒化物結晶基板。 - 前記厚膜の表面の欠陥密度が107/cm2以下であることを特徴とする、請求項1記載の結晶基板。
- 前記厚膜の厚さが1μm以上であり、前記下地層の厚さが50μm以上、200μm以下であることを特徴とする、請求項1または2記載の結晶基板。
- 前記厚膜がフラックス法または気相法によって形成されていることを特徴とする、請求項1~3のいずれか一つの請求項に記載の結晶基板。
- 前記厚膜の表面が研磨面であることを特徴とする、請求項1~4のいずれか一つの請求項に記載の結晶基板。
- 前記下地層を構成する前記13族元素窒化物結晶および前記厚膜を構成する前記13族元素窒化物結晶が窒化ガリウムからなることを特徴とする、請求項1~5のいずれか一つの請求項に記載の結晶基板。
- 請求項1~6のいずれか一つの請求項に記載の結晶基板、および前記結晶基板の前記厚膜上に形成された13族元素窒化物からなる機能層を備えていることを特徴とする、機能素子。
- 前記機能層が発光機能を有することを特徴とする、請求項7記載の機能素子。
- 13族元素窒化物からなる種結晶を更に備えており、この種結晶上に前記結晶基板が設けられていることを特徴とする、請求項7または8記載の機能素子。
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