The invention is related to semiconductor materials, methods, and devices, and more particularly, to non-polar (Al,B,In,Ga)N quantum well and heterostructure materials and devices.
(Note: This application references a number of different patents, applications and/or publications as indicated throughout the specification by one or more reference numbers. A list of these different publications ordered according to these reference numbers can be found below in the section entitled “References.” Each of these publications is incorporated by reference herein.)
Current state of the art (Al,B,In,Ga)N heterostructures and quantum well structures employ c-plane (0001) layers. The total polarization of a III-N film consists of spontaneous and piezoelectric polarization contributions, which both originate from the single polar [0001] axis of the wurtzite nitride crystal structure. Polarization discontinuities which exist at surfaces and interfaces within nitride heterostructures are associated with fixed sheet charges, which in turn produce electric fields. Since the alignment of these internal electric fields coincides with the growth direction of the c-plane (0001) layers, the fields affect the energy bands of device structures.
In quantum wells, the “tilted” energy bands spatially separate electrons and hole wave functions, which reduces the oscillator strength of radiative transitions and red-shifts the emission wavelength. These effects are manifestations of the quantum confined Stark effect (QCSE) and have been thoroughly analyzed for GaN/(Al,Ga)N quantum wells. See References 1-8. Additionally, the large polarization-induced fields are partially screened by dopants and impurities, so the emission characteristics can be difficult to engineer accurately.
The internal fields are also responsible for large mobile sheet charge densities in nitride-based transistor heterostructures. Although these large 2 D electron gases (2 DEGs) are attractive and useful for devices, the polarization-induced fields, and the 2 DEG itself, are difficult to control accurately.
Non-polar growth is a promising means of circumventing the strong polarization-induced electric fields that exist in wurtzite nitride semiconductors. Polarization-induced electric fields do not affect wurtzite nitride semiconductors grown in non-polar directions (i.e., perpendicular to the [0001] axis) due to the absence of polarization discontinuities along non-polar growth directions.
Recently, two groups have grown non-polar GaN/(Al,Ga)N multiple quantum wells (MQWs) via molecular beam epitaxy (MBE) without the presence of polarization-induced electric fields along non-polar growth directions. Waltereit et al. grew m-plane GaN/Al0.1Ga0.9N MQWs on γ-LiAlO2 (100) substrates and Ng grew a-plane GaN/Al0.15Ga0.85N MQW on r-plane sapphire substrates. See References 9-10.
Despite these results, the growth of non-polar GaN orientations remains difficult to achieve in a reproducible manner.
The present invention describes a method for forming non-polar (Al,B,In,Ga)N quantum well and heterostructure materials and devices. First, non-polar (11
Referring now to the drawings in which like reference numbers represent corresponding parts throughout:
a) shows a 2θ-ω x-ray diffraction scan of the 10-period Al0.4Ga0.6N/GaN superlattice, which reveals clearly defined satellite peaks;
b) illustrates the PL spectra of the superlattice characterized in
a) shows a 2θ-ω diffraction scan that identifies the growth direction of the GaN film as (11
b) is a compilation of off-axis φ scans used to determine the in-plane epitaxial relationship between GaN and r-sapphire, wherein the angle of inclination ψ used to access the off-axis reflections is noted for each scan;
c) is a schematic illustration of the epitaxial relationship between the GaN and r-plane sapphire;
a) and 6(b) are cross-sectional and plan-view transmission electron microscopy (TEM) images, respectively, of the defect structure of the a-plane GaN films on r-plane sapphire; and
a) and 7(b) are atomic force microscopy (AFM) amplitude and height images, respectively, of the surface of the as-grown a-plane GaN films.
In the following description of the preferred embodiment, reference is made to the accompanying drawings which form a part hereof, and in which is shown by way of illustration a specific embodiment in which the invention may be practiced. It is to be understood that other embodiments may be utilized and structural changes may be made without departing from the scope of the present invention.
Overview
The purpose of the present invention is to provide a method for producing non-polar (Al,B,In,Ga)N quantum well and heterostructure materials and devices, using non-polar (11
The growth of device-quality non-polar (11
The present invention focuses on the subsequent growth of (Al,B,In,Ga)N quantum wells and heterostructures on the (11
Potential devices to be deposited on non-polar (11
Process Steps
Block 100 represents loading of a sapphire substrate into a vertical, close-spaced, rotating disk, MOCVD reactor. For this step, epi-ready sapphire substrates with surfaces crystallographically oriented within +/−2° of the sapphire r-plane (1
Block 102 represents annealing the sapphire substrate in-situ at a high temperature (>1000° C.), which improves the quality of the substrate surface on the atomic scale. After annealing, the substrate temperature is reduced for the subsequent low temperature nucleation layer deposition.
Block 104 represents depositing a thin, low temperature, low pressure, nitride-based nucleation layer as a buffer layer on the sapphire substrate. Such layers are commonly used in the heteroepitaxial growth of c-plane (0001) nitride semiconductors. In the preferred embodiment, the nucleation layer is comprised of, but is not limited to, 1-100 nanometers (nm) of GaN deposited at approximately 400-900° C. and 1 atm.
After depositing the nucleation layer, the reactor temperature is raised to a high temperature, and Block 106 represents growing the epitaxial (11
Upon completion of the high temperature growth step, Block 108 represents cooling the epitaxial (11
Finally, Block 110 represents non-polar (Al,B,In,Ga)N layers, with differing alloy compositions and hence differing electrical properties, being grown on the non-polar (11
The quantum wells employ alternating layers of different bandgap such that “wells” are formed in the structure's energy band profile. The precise number of layers in the structure depends on the number of quantum wells desired. Upon excitation, electrons and holes accumulate in the wells of the conduction and valence bands, respectively. Band-to-band recombination occurs in the well layers since the density-of-states is highest at these locations. Thus, quantum wells can be engineered according to the desired emission characteristics and available epitaxial growth capabilities.
The nominal thickness and composition of the layers successfully grown on the non-polar (11
8 nm Si-doped In0.03GaN barrier
1.5, 2.5, or 5 nm In0.1GaN well
Moreover, the above Blocks may be repeated as necessary. In one example, Block 110 was repeated 5 times to form an MQW structure that was capped with GaN to maintain the integrity of the (In,Ga)N layers. In this example, the layers comprising the MQW structure were grown via MOCVD at a temperature of 825° C. and atmospheric pressure.
The luminescence characteristics of this structure indicate that polarization-induced electric fields do not affect the band profiles, and the quantum wells can be considered polarization-free. For example,
Further,
In addition to (In,Ga)N quantum wells, heterostructures containing (Al,Ga)N/GaN superlattices may also be grown on the non-polar (11
9 nm Al0.4GaN barrier
In one example, Block 110 was repeated 10 times to form a 10-period Al0.4Ga0.6N/GaN superlattice that was terminated with a 11 nm GaN well layer. The superlattice was grown via MOCVD at conditions similar to those employed for the underlying template layer: ˜1100° C. growth temperature, ˜0.1 atm growth pressure, 38 μmol/min Al flow, 20 μmol/min Ga flow, and 40,000 μmol/min N flow. The Al flow was simply turned off to form the GaN well layers. Successful growth conditions are not strictly defined by the values presented above. Similar to the (In,Ga)N quantum wells, the luminescence characteristics of the superlattice described above indicate that polarization fields do not affect the structure.
a) shows a 2θ-ω x-ray diffraction scan of the 10-period Al0.4Ga0.6N/GaN superlattice, which reveals clearly defined satellite peaks, while
Experimental Results for as-Grown GaN
The crystallographic orientation and structural quality of the as-grown GaN films and r-plane sapphire were determined using a Philips™ four-circle, high-resolution, x-ray diffractometer (HR-XRD) operating in receiving slit mode with four bounce Ge(220)-monochromated Cu Kα radiation and a 1.2 mm slit on the detector arm. Convergent beam electron diffraction (CBED) was used to determine the polarity of the a-GaN films with respect to the sapphire substrate. Plan-view and cross-section transmission electron microscopy (TEM) samples, prepared by wedge polishing and ion milling, were analyzed to define the defect structure of a-GaN. A Digital Instruments D3000 Atomic Force Microscope (AFM) in tapping mode produced images of the surface morphology.
a) shows a 2θ-ω diffraction scan that identifies the growth direction of the GaN film as (11
b) is a compilation of off-axis φ scans used to determine the in-plane epitaxial relationship between GaN and r-sapphire, wherein the angle of inclination ψ used to access the off-axis reflections is noted for each scan. Having confirmed the a-plane growth surface, off-axis diffraction peaks were used to determine the in-epitaxial relationship between the GaN and the r-sapphire. Two sample rotations φ and ψ were adjusted in order to bring off-axis reflections into the scattering plane of the diffractometer, wherein φ is the angle of rotation about the sample surface normal and ψ is the angle of sample tilt about the axis formed by the intersection of the Bragg and scattering planes. After tilting the sample to the correct ψ for a particular off-axis reflection, φ scans detected GaN (10
c) is a schematic illustration of the epitaxial relationship between the GaN and r-plane sapphire. To complement the x-ray analysis of the crystallographic orientation, the a-GaN polarity was determined using CBED. The polarity's sign is defined by the direction of the polar Ga—N bonds aligned along the GaN c-axis; the positive c-axis [0001] points from a gallium atom to a nitrogen atom. Consequently, a gallium-face c-GaN film has a [0001] growth direction, while a nitrogen-face c-GaN crystal has a [000
a) and 6(b) are cross-sectional and plan-view TEM images, respectively, of the defect structure of the a-plane GaN films on an r-plane sapphire substrate. These images reveal the presence of line and planar defects, respectively. The diffraction conditions for
The cross-sectional TEM image in
In addition to line defects, the plan view TEM image in
Omega rocking curves were measured for both the GaN on-axis (11
a) and 7(b) are AFM amplitude and height images, respectively, of the surface of the as-grown a-plane GaN film. The surface pits in the AFM amplitude image of
Although optically specular with a surface RMS roughness of 2.6 nm, the a-GaN growth surface is pitted on a sub-micron scale, as can be clearly observed in the AFM amplitude image shown in
In addition to small surface pits aligned along GaN c-axis [0001], the AFM height image in
The following references are incorporated by reference herein:
This concludes the description of the preferred embodiment of the present invention. The following describes some alternative embodiments for accomplishing the present invention.
For example, variations in non-polar (Al,In,Ga)N quantum wells and heterostructures design and MOCVD growth conditions may be used in alternative embodiments. Moreover, the specific thickness and composition of the layers, in addition to the number of quantum wells grown, are variables inherent to quantum well structure design and may be used in alternative embodiments of the present invention.
Further, the specific MOCVD growth conditions determine the dimensions and compositions of the quantum well structure layers. In this regard, MOCVD growth conditions are reactor dependent and may vary between specific reactor designs. Many variations of this process are possible with the variety of reactor designs currently being using in industry and academia.
Variations in conditions such as growth temperature, growth pressure, V/III ratio, precursor flows, and source materials are possible without departing from the scope of the present invention. Control of interface quality is another important aspect of the process and is directly related to the flow switching capabilities of particular reactor designs. Continued optimization of the growth conditions will result in more accurate compositional and thickness control of the integrated quantum well layers described above.
In addition, a number of different growth methods other than MOCVD could be used in the present invention. For example, the growth method could also be molecular beam epitaxy (MBE), liquid phase epitaxy (LPE), hydride vapor phase epitaxy (HVPE), sublimation, or plasma-enhanced chemical vapor deposition (PECVD).
Further, although non-polar a-plan GaN thin films are described herein, the same techniques are applicable to non-polar m-plane GaN thin films. Moreover, non-polar InN, AlN, and AlInGaN thin films could be created instead of GaN thin films.
Finally, substrates other than sapphire substrate could be employed for non-polar GaN growth. These substrates include silicon carbide, gallium nitride, silicon, zinc oxide, boron nitride, lithium aluminate, lithium niobate, germanium, aluminum nitride, and lithium gallate.
In summary, the present invention describes a method for forming non-polar (Al,B,In,Ga)N quantum well and heterostructure materials and devices. First, non-polar (11
The foregoing description of one or more embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Many modifications and variations are possible in light of the above teaching. It is intended that the scope of the invention be limited not by this detailed description, but rather by the claims appended hereto.
This application is a continuation under 35 U.S.C. Section 120 of co-pending and commonly-assigned U.S. Utility patent application Ser. No. 11/472,033, filed on Jun. 21, 2006, by Michael D. Craven, Stacia Keller, Steven P. DenBaars, Tal Margalith, James S. Speck, Shuji Nakamura, and Umesh K. Mishra, entitled “NON-POLAR (Al,B,In,Ga)N QUANTUM WELL AND HETEROSTRUCTURE MATERIALS AND DEVICES” attorneys' docket no. 30794.101-US-D1 (2002-301-3), which application is a divisional application claiming the benefit under 35 U.S.C. Section 120 and Section 121 of U.S. Utility patent application Ser. No. 10/413,690, filed on Apr. 15, 2003, now U.S. Pat. No. 7,091,514, issued Aug. 15, 2006, by Michael D. Craven, Stacia Keller, Steven P. DenBaars, Tal Margalith, James S. Speck, Shuji Nakamura, and Umesh K. Mishra, entitled “NON-POLAR (Al,B,In,Ga)N QUANTUM WELL AND HETEROSTRUCTURE MATERIALS AND DEVICES” attorneys' docket no. 30794.101-US-U1 (2002-301-2), which application claims the benefit under 35 U.S.C. §119(e) of the following co-pending and commonly-assigned U.S. Provisional Patent Application Ser. No. 60/372,909, entitled “NON-POLAR GALLIUM NITRIDE BASED THIN FILMS AND HETEROSTRUCTURE MATERIALS,” filed on Apr. 15, 2002, by Michael D. Craven, Stacia Keller, Steven P. DenBaars, Tal Margalith, James S. Speck, Shuji Nakamura, and Umesh K. Mishra, attorneys docket number 30794.95-US-P1, all of which applications are incorporated by reference herein. This application is related to the following co-pending and commonly-assigned United States Utility patent applications: Ser. No. 10/413,691, entitled “NON-POLAR A-PLANE GALLIUM NITRIDE THIN FILMS GROWN BY METALORGANIC CHEMICAL VAPOR DEPOSITION,” filed Apr. 15, 2003, by Michael D. Craven and James S. Speck, attorneys docket number 30794.100-US-U1; and Ser. No. 10/413,913, entitled “DISLOCATION REDUCTION IN NON-POLAR GALLIUM NITRIDE THIN FILMS,” Apr. 15, 2003, now issued U.S. Pat. No. 6,900,070 issued May 31, 2005, by Michael D. Craven, Stacia Keller, Steven P. DenBaars, Tal Margalith, James S. Speck, Shuji Nakamura, and Umesh K. Mishra, attorneys docket number 30794.102-US-U1; both of which applications are incorporated by reference herein.
Number | Date | Country | |
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60372909 | Apr 2002 | US |
Number | Date | Country | |
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Parent | 10413690 | Apr 2003 | US |
Child | 11472033 | US |
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Parent | 11472033 | Jun 2006 | US |
Child | 13099834 | US |