Template for epitaxial growth, method for producing the same, and nitride semiconductor device
09556535 ยท 2017-01-31
Assignee
Inventors
Cpc classification
H01L21/20
ELECTRICITY
C30B31/08
CHEMISTRY; METALLURGY
H10H20/815
ELECTRICITY
H10H20/01335
ELECTRICITY
H10H20/812
ELECTRICITY
H01L21/0262
ELECTRICITY
H01S2301/173
ELECTRICITY
H01L21/02614
ELECTRICITY
C30B25/183
CHEMISTRY; METALLURGY
International classification
H01L33/00
ELECTRICITY
H01L21/20
ELECTRICITY
H01S5/323
ELECTRICITY
H01S5/02
ELECTRICITY
H01L33/06
ELECTRICITY
C30B31/08
CHEMISTRY; METALLURGY
C30B29/40
CHEMISTRY; METALLURGY
H01L33/14
ELECTRICITY
Abstract
The present invention provides a method for producing a template for epitaxial growth, the method including: a surface treatment step of dispersing Ga atoms on a surface of a sapphire substrate; and an AlN growth step of epitaxially growing an AlN layer on the sapphire substrate, wherein in a Ga concentration distribution in a depth direction perpendicular to the surface of the sapphire substrate in an internal region of the AlN layer excluding a near-surface region up to a depth of 100 nm from the surface of the AlN layer, which is obtained by secondary ion mass spectrometry, a position in the depth direction where the Ga concentration takes the maximum value is present in a near-interface region located between the interface of the sapphire substrate and a position at 400 nm spaced apart from the interface to the AlN layer side, and the maximum value of the Ga concentration is 310.sup.17 atoms/cm.sup.3 or more and 210.sup.20 atoms/cm.sup.3 or less.
Claims
1. A method for producing a template having an AlN layer on a surface of a sapphire substrate and used as an underlayer for epitaxially growing a GaN-family compound semiconductor layer, the method comprising: a surface treatment step of dispersing Ga atoms on a surface of a sapphire substrate; and an AlN growth step of epitaxially growing an AlN layer on the sapphire substrate, wherein in a Ga concentration distribution in a depth direction perpendicular to the surface of the sapphire substrate in an internal region of the AlN layer excluding a near-surface region up to a depth of 100 nm from the surface of the AlN layer, which is obtained by secondary ion mass spectrometry, a position in the depth direction where the Ga concentration takes a maximum value is present in a near-interface region located between the surface of the sapphire substrate and a position at 400 nm spaced apart from the surface of the sapphire substrate to the AlN layer side, and the maximum value of the Ga concentration is 310.sup.17 atoms/cm.sup.3 or more and 210.sup.20 atoms/cm.sup.3 or less.
2. The method for producing a template according to claim 1, wherein a primary ion species used in the secondary ion mass spectrometry is O.sub.2.sup.+.
3. The method for producing a template according to claim 1, wherein the AlN growth step is started at any of the following timings: after a completion of the surface treatment step, simultaneously with a start of the surface treatment step, or in a middle of the surface treatment step.
4. The method for producing a template according to claim 3, wherein a primary ion species used in the secondary ion mass spectrometry is O.sub.2.sup.+.
5. The method for producing a template according to claim 1, wherein in the surface treatment step, a compound as a material of Ga is supplied to a growth chamber for performing the AlN growth step.
6. The method for producing a template according to claim 5, wherein a primary ion species used in the secondary ion mass spectrometry is O.sub.2.sup.+.
7. The method for producing a template according to claim 5, wherein the AlN growth step is started at any of the following timings: after a completion of the surface treatment step, simultaneously with a start of the surface treatment step, or in a middle of the surface treatment step.
8. The method for producing a template according to claim 7, wherein a primary ion species used in the secondary ion mass spectrometry is O.sub.2+.
9. A template for epitaxial growth comprising: a sapphire substrate having Ga atoms dispersed on a surface thereof; and an AlN layer epitaxially grown on the sapphire substrate, wherein in a Ga concentration distribution in a depth direction perpendicular to the surface of the sapphire substrate in an internal region of the AlN layer excluding a near-surface region up to a depth of 100 nm from the surface of the AlN layer, which is obtained by secondary ion mass spectrometry, a position in the depth direction where the Ga concentration takes a maximum value is present in a near-interface region located between the surface of the sapphire substrate and a position at 400 nm spaced apart from the surface of the sapphire substrate to the AlN layer side, and the maximum value of the Ga concentration is 310.sup.17 atoms/cm.sup.3 or more and 210.sup.20 atoms/cm.sup.3 or less.
10. A nitride semiconductor device comprising: the template for epitaxial growth according to claim 9; and at least one GaN-family compound semiconductor layer epitaxially grown on the template.
11. The template for epitaxial growth according to claim 9, wherein a primary ion species used in the secondary ion mass spectrometry is O.sub.2.sup.+.
12. A nitride semiconductor device comprising: the template for epitaxial growth according to claim 11; and at least one GaN-family compound semiconductor layer epitaxially grown on the template.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1)
(2)
(3)
(4)
(5)
(6)
(7)
MODE FOR CARRYING OUT THE INVENTION
(8) The following describes embodiments of a method for producing a template for epitaxial growth (hereinafter, sometimes referred to as the present production method) according to the present invention and a template for epitaxial growth included in a nitride semiconductor device (hereinafter, sometimes referred to as the present template) according to the present invention with reference to the drawings.
(9)
(10) In any of the first to third production methods, a sapphire substrate 2 is first prepared and housed in a reaction chamber (not shown) for epitaxially growing an AlN layer 3 (see
(11) In the first production method, TMG (trimethylgallium) as a material (precursor) of Ga for MOVPE is then supplied to the reaction chamber at a predetermined flow rate and a predetermined time, and Ga atoms 4 are dispersed on the surface of the sapphire substrate 2 (surface treatment step: see
(12) In the second production method, TMG (trimethylgallium) as a material (precursor) of Ga for MOVPE is then supplied to the reaction chamber at a predetermined flow rate and a predetermined time, and Ga atoms 4 are dispersed on the surface of the sapphire substrate 2 (surface treatment step: see
(13) In the third production method, TMG (trimethylgallium) as a material (precursor) of Ga for MOVPE is then supplied to the reaction chamber at a predetermined flow rate and a predetermined time, and Ga atoms 4 are dispersed on the surface of the sapphire substrate 2 (surface treatment step: see
(14) As shown in
(15) Thus, a template for epitaxial growth having a fine and flat surface and no cracks (the present template 1) is provided by the present production method.
(16) The thickness of the AlN layer 3 is, for example, about 1 m to 10 m. The growth temperature in the AlN growth step is set higher (for example, at 1230 C. to 1350 C.) than the crystallization temperature of AlN. The pressure is set about 50 Torr or less. In this embodiment, TMA (trimethylaluminum) and NH.sub.3 (ammonia) as the materials (precursors) of Al and N are continuously supplied within the range of a predetermined flow ratio (NH.sub.3/TMA). Since the optimal value of each of the above setting conditions varies depending on the device such as a reaction chamber to be used, it is appropriately adjusted in accordance with the device to be used.
(17) In the second and third production methods, the temperature and pressure conditions in the surface treatment step are similar to those in the AlN growth step. In the first and second production methods, the temperature and pressure conditions prior to the AlN growth step may be similar to those in the AlN growth step. For example, the pressure may be set about 100 Torr instead, which is higher than that in the AlN growth step.
(18) Regarding the samples of the present templates 1 produced by the first to third production methods and the samples produced by similar production methods which are different from the first to third production methods only in terms of TMG supply condition in the surface treatment step (the first to third similar production methods), the evaluation results of the surface morphology will be described below with reference to the drawings. The samples produced by the first to third production methods have good surface morphologies. They are good quality samples in which the maximum value of the Ga concentration is within the preferable range of 310.sup.17 atoms/cm.sup.3 to 210.sup.20 atoms/cm.sup.3. The samples produced by the similar production methods are poor samples whose surface morphology is poor due to occurrence of cracks and in which the maximum value of the Ga concentration is out of the preferable range (less than 310.sup.17 atoms/cm.sup.3 or more than 210.sup.20 atoms/cm.sup.3). For the convenience of explanation, the first production method and the first similar production method are collectively referred to as the first method, the second production method and the second similar production method are collectively referred to as the second method, and the third production method and the third similar production method are collectively referred to as the third method.
(19) In this embodiment, the Ga concentration in the AlN layer 3 is measured by the secondary ion mass spectrometry. In this regard, an oxygen ion (O.sub.2.sup.+) is used as the primary ion species. Generally, in ion mass spectrometry, a cesium ion (Cs+) or an oxygen ion (O.sub.2.sup.+) is used as the primary ion species. In this embodiment, an oxygen ion that reduces the background level of Ga in AlN is used. When the primary ion species is a cesium ion, the background level of Ga in AlN is 210.sup.17 to 310.sup.17 atoms/cm.sup.3. Thus, it is impossible to accurately measure the Ga concentration around the lower limit of the preferable range of the maximum value of the Ga concentration or lower than the lower limit. On the other hand, when the primary ion species is an oxygen ion, the background level of Ga in AlN is less than 110.sup.17 atoms/cm.sup.3 (about 4 to 810.sup.16 atoms/cm.sup.3). Thus, it is possible to accurately measure the Ga concentration around the lower limit of the preferable range or lower than the lower limit.
(20) The maximum value of the Ga concentration in the AlN layer 3 is calculated excluding the near-surface region up to a depth of 100 nm from the surface of the AlN layer 3. This is because the Ga concentration in the near-surface region which is measured by the secondary ion mass spectrometry may not be accurately measured due to influences of substances such as oxides adhered to the surface of the AlN layer 3 and the charge-up of the surface.
(21) As a standard for specifying the above-noted near-interface region, the depth (position in the depth direction) of the interface between the sapphire substrate 2 and the AlN layer 3 can be grasped from the nitrogen concentration measured by the secondary ion mass spectrometry, because of large changes in the nitrogen concentration at the interface. However, an error (about several 10 nm to 100 nm) may occur in the depth of the interface due to a matrix effect. Thus, in this embodiment, the near-interface region is 400 nm long, which is longer than the error, and the maximum value of the Ga concentration is used as a standard for evaluation. Accordingly, even if the interface position for specifying the near-interface region is shifted to the inside of the sapphire substrate 2 due to the error and the Ga concentration at the interface is seemingly a low value, it is possible to correctly evaluate the relationship between the Ga concentration in the near-interface region and the surface morphology of the present template 1.
(22)
(23) In the surface treatment step (the first method) of each of the samples #11 to #17, TMG was supplied at a flow rate ranging from 0.005 sccm to 0.1 sccm for 30 seconds. In the surface treatment step (the second method) of each of the samples #21 to #23, TMG was supplied at a flow rate ranging from 0.005 sccm to 0.4 sccm for 30 seconds before the start of the AlN growth step, and TMG was supplied at a flow rate ranging from 0.005 sccm to 0.1 sccm for 1 minute or 10 minutes after the start of the AlN growth step. In the surface treatment step (the third method) of each of the samples #31 to #39, TMG was supplied at a flow rate ranging from 0.005 sccm to 20 sccm for 1 minute or 10 minutes. In each of the samples, the AlN growth rate in the AlN growth step is about 1.2 m/h, and the target thickness of the AlN layer 3 is 2 m. However, the actual thickness of the AlN layer 3 varies to some extent among the samples. In the surface treatment step of each of the samples #21 to #23 and the samples #31 to #39, during the overlap with the AlN growth step of 1 minute or 10 minutes, the AlN layer 3 grows at a growth rate of about 1.2 m/h. Therefore, the thickness of the layer grown in the period is about 20 nm or about 200 nm. The grown part of the AlN layer 3 is present in the near-interface region.
(24) The results shown in
(25) Subsequently, the secondary ion mass spectrometry results of the Ga concentration distribution in the depth direction of the AlN layer 3 (direction perpendicular to the surface of the sapphire substrate 2) regarding the sample #15 (good quality sample) of the samples produced by the first production method, the sample #17 (poor sample) produced by the first similar production method, the samples #32 to #34 (good quality samples) of the samples produced by the third production method, and the sample #39 (poor sample) produced by the third similar production method will be described with reference to
(26) In the samples #15 and #17 produced by the first method, the supply of TMG before the AlN growth step is suppressed in each case. The flow rate of the sample #15 is set 5 times as high as that of the sample #17.
(27) As shown in
(28) On the other hand, as shown in
(29) In the samples #32 to #34 and #39 produced by the third method, the supply of TMG in the surface treatment step is significantly changed so that the maximum value of the Ga concentration in the AlN layer 3 is a value slightly higher than the lower limit of the preferable range (310.sup.17 to 210.sup.20 atoms/cm.sup.3), a value slightly lower than the upper limit of the preferable range or a value higher than the upper limit of the preferable range. Specifically, the supply of TMG is increased in order of the samples #32, #33, #34, and #39.
(30) As shown in
(31) As shown in
(32) As shown in
(33) As shown in
(34) The measurement results of Ga concentration shown in
(35) Further, in each of the good quality samples #15 and #32 to #34, the depth for the maximum value of the Ga concentration in the internal region of the AlN layer 3 is indeed in the near-interface region. A more detailed observation shows that the depth is present in a region closer to the interface that is located from the interface between the sapphire substrate 2 and the AlN layer 3 to a position at about 300 nm spaced apart from the interface to the side of the AlN layer 3. Even if the determined interface position has an error of about 100 nm, the depth for the maximum value of the Ga concentration is certainly present in the near-interface region. Further, the Ga concentration distribution of each of the good quality samples #15 and #32 to #34 supports the fact that Ga atoms are mostly present in the interface between the sapphire substrate 2 and the AlN layer 3.
(36) The lower limit of the preferable range of the maximum value of the Ga concentration may be set within the range of 310.sup.17 atoms/cm.sup.3 to 610.sup.17 atoms/cm.sup.3. For example, the lower limit of the preferable range is preferably 410.sup.17 atoms/cm.sup.3 or 510.sup.17 atoms/cm.sup.3. The upper limit of the preferable range of the maximum value of the Ga concentration may be set within the range of 1.110.sup.20 atoms/cm.sup.3 to 210.sup.20 atoms/cm.sup.3. For example, it is preferably 1.510.sup.20 atoms/cm.sup.3 or 1.210.sup.20 atoms/cm.sup.3. The lower and upper limits may be combined arbitrarily.
(37) It has been described that, in Ga concentration distribution of the samples produced by the first production method and the good quality samples having no cracks produced by the third production method, a position in the depth direction where the Ga concentration takes the maximum value in an internal region excluding the near-surface region of the AlN layer 3 is present in the above-noted near-interface region, and the maximum value of the Ga concentration is present within the preferable range of 310.sup.17 atoms/cm.sup.3 or more and 210.sup.20 atoms/cm.sup.3 or less. In the above-noted description, the Ga concentration distribution of the sample produced by the second production method is not measured. However, in the second production method, as is clear from the above-noted description, the surface treatment step has an eclectic structure including both the surface treatment step of the first production method and the surface treatment step of the third production method, and therefore, it is obvious that when the supply of TMG is appropriately adjusted, it is possible to achieve the condition that a position in the depth direction where the Ga concentration takes the maximum value in an internal region excluding the near-surface region of the AlN layer 3 is present in the above-noted near-interface region, and the maximum value of the Ga concentration is present within the preferable range of 310.sup.17 atoms/cm.sup.3 or more and 210.sup.20 atoms/cm.sup.3 or less, similarly to the case of the first and third production methods.
(38) The present production method and present template have been described above in detail. The characteristics of the present invention lie in an underlayer for epitaxially growing a GaN-family compound semiconductor layer including a sapphire substrate 2 and an AlN layer 3 epitaxially grown thereon, and a method for producing the same, wherein in a depth direction distribution of Ga concentration in an internal region of the AlN layer 3 excluding the near-surface region, which is obtained by secondary ion mass spectrometry, a position in the depth direction where the Ga concentration takes the maximum value is present in the near-interface region, and the maximum value of the Ga concentration is 310.sup.17 atoms/cm.sup.3 or more and 210.sup.20 atoms/cm.sup.3 or less. The above-noted production method and conditions are merely an example for description, and these conditions and the like may be appropriately modified without departing from the present invention including the above characteristics.
(39) In the above-noted embodiments, the MOVPE method is assumed as the method of epitaxially growing the AlN layer 3. As the surface treatment step of dispersing Ga atoms 4 on the surface of the sapphire substrate 2, in the first production method, it has been described that TMG as a material (precursor) of Ga for MOVPE is supplied to the reaction chamber at a predetermined flow rate and a predetermined time before the AlN growth step. In the second production method, it has been described that the supply of the TMG is performed before and after the start of the AlN growth step. In the third production method, it has been described that the supply of the TMG is started simultaneously with the start of the AlN growth step. However, the method of epitaxially growing the AlN layer 3 is not limited to MOVPE. For example, the hydride VPE (vapor phase epitaxy) method may be applied as the epitaxial growth method. Further, the surface treatment step is not limited to the methods exemplified in the above-noted first to third production methods as long as it is a method capable of dispersing the Ga atoms 4 on the surface of the sapphire substrate 2 and satisfying the condition that the depth where the Ga concentration takes the maximum value is present in the near-interface region and the maximum value of the Ga concentration is within the preferable range. In the above-noted first to third production methods, it has been described that the surface treatment step is started after the sapphire substrate 2 is housed in the reaction chamber. However, the same effect can also be produced by, for example, previously supplying an appropriate amount of a material of Ga to the reaction chamber before housing the sapphire substrate 2 in the reaction chamber.
(40) Subsequently, the nitride semiconductor device produced by epitaxially growing a GaN-familiy compound semiconductor layer on the present template 1 produced by the present production method will be described. Depending on the laminated structure of the GaN-family compound semiconductor layer formed on the present template 1, an element structure such as a light-emitting diode, a semiconductor laser, a switching element or an amplifying element is formed. The present nitride semiconductor device features the present template 1 used as an underlayer. The element structure formed thereon is not limited to a specific structure. In the case of the light-emitting diode, a light emitting diode as the nitride semiconductor device is produced by, for example, laminating the element structure which is the upper part above the ELO-AlN layer 103 shown in
INDUSTRIAL APPLICABILITY
(41) The template for epitaxial growth and the method for producing the same according to the present invention are applicable to produce a GaN-family nitride semiconductor device such as a light-emitting diode and a semiconductor laser.
EXPLANATION OF REFERENCES
(42) 1: Template for epitaxial growth 2: Sapphire substrate 3: AlN layer 4: Ga atom