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US20070128844A1 - Non-polar (a1,b,in,ga)n quantum wells - Google Patents

Non-polar (a1,b,in,ga)n quantum wells Download PDF

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US20070128844A1
US20070128844A1 US10/582,390 US58239003A US2007128844A1 US 20070128844 A1 US20070128844 A1 US 20070128844A1 US 58239003 A US58239003 A US 58239003A US 2007128844 A1 US2007128844 A1 US 2007128844A1
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Michael Craven
Steven Denbaars
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Japan Science and Technology Agency
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Assigned to REGENTS OF THE UNIVERSITY OF CALIFORNIA, THE reassignment REGENTS OF THE UNIVERSITY OF CALIFORNIA, THE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DENBAARS, STEVEN P., CRAVEN, MICHAEL D.
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Definitions

  • the invention is related to semiconductor materials, methods, and devices, and more particularly, to non-polar (Al,B,In,Ga)N quantum wells.
  • Nitride crystal growth along non-polar directions provides an efficient means of producing nitride-based quantum structures that are unaffected by these strong polarization-induced electric fields since the polar axis lies within the growth plane of the film.
  • m-plane GaN/AlGaN multiple quantum well (MQW) structures were first demonstrated by plasma-assisted molecular beam epitaxy (MBE) using lithium aluminate substrates [3]. Since this first demonstration, free-standing m-plane GaN substrates grown by hydride vapor phase epitaxy (HVPE) were employed for subsequent epitaxial GaN/AlGaN MQW growths by both MBE [4] and metalorganic chemical vapor deposition (MOCVD) [5].
  • HVPE hydride vapor phase epitaxy
  • the present invention describes the dependence of a-plane GaN/AlGaN MQW emission on the GaN quantum well width. Moreover, an investigation of a range of GaN well widths for MOCVD-grown a-plane and c-plane MQWs provides an indication of the emission characteristics that are unique to non-polar orientations.
  • the present invention describes a method of fabricating non-polar a-plane GaN/(Al,B,In,Ga)N multiple quantum wells (MQWs).
  • a-plane MQWs were grown on the appropriate GaN/sapphire template layers via metalorganic chemical vapor deposition (MOCVD) with well widths ranging from 20 ⁇ to 70 ⁇ .
  • MOCVD metalorganic chemical vapor deposition
  • the room temperature photoluminescence (PL) emission energy from the a-plane MQWs followed a square well trend modeled using self-consistent Poisson-Schrodinger (SCPS) calculations.
  • Optimal PL emission intensity is obtained at a quantum well width of 52 ⁇ for the a-plane MQWs.
  • FIG. 1 is a flowchart that illustrates the steps of a method for forming non-polar a-plane GaN/(Al,B,In,Ga)N quantum wells according to a preferred embodiment of the present invention.
  • FIG. 2 is a graph of high-resolution x-ray diffraction (HRXRD) scans of simultaneously regrown a-plane (69 ⁇ GaN)/(96 ⁇ Al 0.16 Ga 0.84 N) and c-plane (72 ⁇ GaN)/(98 ⁇ Al 0.16 Ga 0.84 N) MQW stacks.
  • HRXRD high-resolution x-ray diffraction
  • FIGS. 3 ( a ) and ( b ) are graphs of room temperature PL spectra of the (a) a-plane and (b) c-plane GaN/(100 ⁇ Al 0.16 Ga 0.84 N) MQWs with well widths ranging from 20 ⁇ -70 ⁇ .
  • the vertical gray line on each plot denotes a band edge of the bulk GaN layers.
  • FIG. 4 is a graph of the well width dependence of the room temperature PL emission energy of the a-plane and c-plane MQWs.
  • the dotted line is the result of self-consistent Poisson-Schrodinger (SCPS) calculations for a flat-band GaN/(100 ⁇ Al 0.16 Ga 0.84 N) MQW.
  • SCPS Poisson-Schrodinger
  • FIG. 5 is a graph of the normalized room temperature PL intensity plotted as a function of GaN quantum well width for both a-plane and c-plane growth orientations. The data for each orientation is normalized separately, hence direct comparisons between the relative intensities of a-plane and c-plane MQWs are not possible.
  • Non-polar nitride-based semiconductor crystals do not experience the effects of polarization-induced electric fields that dominate the behavior of polar nitride-based quantum structures. Since the polarization axis of a wurtzite nitride unit cell is aligned parallel to the growth direction of polar nitride crystals, internal electric fields are present in polar nitride heterostructures. These “built-in” fields have a detrimental effect on the performance of state-of-the-art optoelectronic and electronic devices. By growing nitride crystals along non-polar directions, quantum structures not influenced by polarization-induced electric fields are realized. Since the energy band profiles of a given quantum well change depending upon the growth orientation, different scientific principles must be applied in order to design high performance non-polar quantum wells. This invention describes the design principles used to produce optimized non-polar quantum wells.
  • FIG. 1 is a flowchart that illustrates the steps of a method for forming quantum wells according to a preferred embodiment of the present invention. The steps of this method grow non-polar a-plane GaN/AlGaN MQWs on a-plane GaN/r-plane sapphire template layers.
  • Block 100 represents loading of a sapphire substrate into a vertical, close-spaced, showerhead MOCVD reactor.
  • epi-ready sapphire substrates with surfaces crystallographically oriented within ⁇ 2° of the sapphire r-plane may be obtained from commercial vendors. No ex-situ preparations need be performed prior to loading the sapphire substrate into the MOCVD reactor, although ex-situ cleaning of the sapphire substrate could be used as a precautionary measure.
  • 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.
  • nitride-based 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.
  • Block 106 represents one or more growing unintentionally doped (UID) a-plane GaN layers to a thickness of approximately 1.5 ⁇ m on the nucleation layer deposited on the substrate.
  • the high temperature growth conditions include, but are not limited to, approximately 1100° C. growth temperature, 0.2 atm or less growth pressure, 30 ⁇ mol per minute Ga flow, and 40,000 ⁇ mol per minute N flow, thereby providing a V/III ratio of approximately 1300).
  • the precursors used as the group III and V sources are trimethylgallium, ammonia and disilane, although alternative precursors could be used as well.
  • growth conditions may be varied to produce different growth rates, e.g., between 5 and 9 ⁇ per second, without departing from the scope of the present invention.
  • Block 108 represents cooling the epitaxial a-plane GaN layers down under a nitrogen overpressure.
  • Block 110 represents one or more (Al,B,In,Ga)N layers being grown on the a-plane GaN layers.
  • these grown layers comprise ⁇ 100 ⁇ Al 0.16 Ga 0.84 N barriers doped with an Si concentration of ⁇ 2 ⁇ 10 18 cm ⁇ 3 .
  • the above Blocks may be repeated as necessary. In one example, Block 110 was repeated 10 times to form UID GaN wells ranging in width from approximately 20 ⁇ to approximately 70 ⁇ .
  • non-polar nitride quantum wells flat energy band profiles exist and the QCSE is not present. Consequently, non-polar quantum well emission is expected to follow different trends as compared to polar quantum wells. Primarily, non-polar quantum wells exhibit improved recombination efficiency, and intense emission from thicker quantum wells is possible. Moreover, the quantum well width required for optimal non-polar quantum well emission is larger than for polar quantum wells.
  • the following describes the room temperature PL characteristics of non-polar GaN/( ⁇ 100 ⁇ Al 0.16 Ga 0.84 N) MQWs in comparison to c-plane structures as a function of quantum well width.
  • 10-period a-plane and c-plane MQWs structures were simultaneously regrown on the appropriate GaN/sapphire template layers via MOCVD with well widths ranging from approximately 20 ⁇ to 70 ⁇ .
  • FIG. 2 is a graph of HRXRD scans of simultaneously regrown a-plane 69 ⁇ GaN/96 ⁇ Al 0.16 Ga 0.84 N and c-plane 72 ⁇ GaN/98 ⁇ Al 0.16 Ga 0.84 N MQW stacks.
  • the HRXRD profiles provide a qualitative comparison of the MQW interface quality through the FWHM of the satellite peaks.
  • the on-axis 2 ⁇ - ⁇ scans of the a-plane and c-plane structures were taken about the GaN (11 2 0) and (0004) reflections, respectively.
  • Analysis of the x-ray profiles yields both the aluminum composition x of the Al x Ga 1-x N barriers and the quantum well dimensions (well and barrier thickness), which agree within 7% for the simultaneously grown a-plane and c-plane samples indicating a mass transport limited MOCVD growth regime.
  • Both HRXRD profiles reveal superlattice (SL) peaks out to the second order in addition to strong reflections from the GaN layers.
  • the FWHMs of the SL peaks provide a qualitative metric of the quantum well interface quality [10]; therefore, from the scans shown in FIG.
  • FIGS. 3 ( a ) and ( b ) are graphs of room temperature PL spectra of the (a) a-plane and (b) c-plane GaN/(100 ⁇ Al 0.16 Ga 0.84 N) MQWs with well widths ranging from ⁇ 20 ⁇ to ⁇ 70 ⁇ .
  • the vertical gray line on each plot denotes the bulk GaN band edge.
  • the MQW PL emission shifts to longer wavelengths (equivalently, the PL emission decreases) with increasing quantum well width as the quantum confinement is reduced.
  • the c-plane MQW emission energy red-shifts below the GaN band edge when the GaN quantum well width is increased from 38 ⁇ to 50 ⁇ .
  • the appearance of c-GaN buffer emission implies that the c-plane template has a lower native point defect density than the a-plane template.
  • yellow band emission was observed for both the non-polar and polar MQWs; therefore, the origin of deep trap levels is most likely the growth conditions required to maintain the a-plane morphology and not a characteristic of the non-polar orientation.
  • the two primary features of the PL emission spectra, the emission energy and the emission intensity, are summarized in FIGS. 4 and 5 , respectively, as functions of quantum well width.
  • the emission energy decreases with increasing well width due to quantum confinement effects.
  • FIG. 4 is a graph of the well width dependence of the room temperature PL emission energy of the a-plane and c-plane MQWs.
  • the a-plane MQW emission is blue-shifted with respect to the bulk GaN band edge and the blue-shift increases with decreasing well width as quantum confinement raises the quantum well's ground-state energy.
  • the a-plane MQW emission energy trend is modeled accurately using square well SCPS calculations [11] shown as the dotted line in FIG. 4 .
  • the agreement between theory and experiment confirms that emission from non-polar MQWs is not influenced by polarization-induced electric fields. Despite this agreement, the theoretical model increasingly over-estimates the experimental data with decreasing quantum well width by 15 to 35 meV.
  • FIG. 4 shows the dramatic red-shift in c-plane MQW emission with increasing well width, a widely observed trend dictated by the QCSE [14-18].
  • the experimental c-plane MQW emission energy trend agrees with the model of the polar QW ground state proposed by Grandjean et al. [13]. Interpolating the experimental data, the emission from c-plane MQWs with GaN well widths greater than ⁇ 43 ⁇ is below the bulk GaN band edge.
  • FIG. 5 is a graph of the normalized room temperature PL emission intensity plotted as a function of GaN quantum well width for both a-plane and c-plane growth orientations.
  • the data for each orientation is normalized separately, hence direct comparisons between the relative intensities of a-plane MQWs and c-plane MQWs are not possible. Since the microstructural quality of the template layers is substantially different, a direct comparison between a-and c-plane MQW emission intensity would be inconclusive.
  • a maximum a-plane MQW emission intensity is associated with an optimal quantum well width of 52 ⁇ , while the maximum c-plane emission intensity is observed for 28 ⁇ -wide wells.
  • optimal emission intensity is obtained from relatively thin polar GaN quantum wells (20 ⁇ -35 ⁇ ) depending on the thickness and composition of the AlGaN barrier layers [13]. The balance between reduced recombination efficiency in thick wells and the reduced recombination due to increased nonradiative transitions at heterointerfaces and extension of electron wavefunctions outside of thin wells [19] determines the optimal c-plane well width.
  • the optimal well width is determined by material quality, interface roughness, and the excitonic Bohr radius. Although the interface roughness of the a-plane structures is greater than the c-plane, the advantageous effects of a non-polar orientation are apparent. Also note that, with improved non-polar surface and interface quality, the optimal well width will most likely shift from the optimal width observed for these samples.
  • non-polar (Al,In,Ga)N quantum wells and heterostructures design and MOCVD growth conditions may be used in alternative embodiments.
  • 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.
  • MOCVD growth conditions determine the dimensions and compositions of the quantum well structure layers.
  • 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.
  • 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).
  • MBE molecular beam epitaxy
  • LPE liquid phase epitaxy
  • HVPE hydride vapor phase epitaxy
  • PECVD plasma-enhanced chemical vapor deposition
  • substrates other than sapphire could be employed. These substrates include silicon carbide, gallium nitride, silicon, zinc oxide, boron nitride, lithium aluminate, lithium niobate, germanium, aluminum nitride, and lithium gallate.

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US10/413,690 US7091514B2 (en) 2002-04-15 2003-04-15 Non-polar (Al,B,In,Ga)N quantum well and heterostructure materials and devices
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US20110037052A1 (en) * 2006-12-11 2011-02-17 The Regents Of The University Of California Metalorganic chemical vapor deposition (mocvd) growth of high performance non-polar iii-nitride optical devices
US8178373B2 (en) 2006-12-11 2012-05-15 The Regents Of The University Of California Metalorganic chemical vapor deposition (MOCVD) growth of high performance non-polar III-nitride optical devices
US8956896B2 (en) 2006-12-11 2015-02-17 The Regents Of The University Of California Metalorganic chemical vapor deposition (MOCVD) growth of high performance non-polar III-nitride optical devices
US9130119B2 (en) 2006-12-11 2015-09-08 The Regents Of The University Of California Non-polar and semi-polar light emitting devices

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