WO2008094464A2 - Thick pseudomorphic nitride epitaxial layers - Google Patents

Thick pseudomorphic nitride epitaxial layers Download PDF

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WO2008094464A2
WO2008094464A2 PCT/US2008/001003 US2008001003W WO2008094464A2 WO 2008094464 A2 WO2008094464 A2 WO 2008094464A2 US 2008001003 W US2008001003 W US 2008001003W WO 2008094464 A2 WO2008094464 A2 WO 2008094464A2
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layer
approximately
strained
strained layer
thickness
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WO2008094464A3 (en
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Leo J. Schowalter
Joseph A. Smart
James R. Grandusky
Shiwen Liu
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Crystal IS Inc
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02612Formation types
    • H01L21/02617Deposition types
    • H01L21/0262Reduction or decomposition of gaseous compounds, e.g. CVD
    • HELECTRICITY
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    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02367Substrates
    • H01L21/0237Materials
    • H01L21/02387Group 13/15 materials
    • H01L21/02389Nitrides
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    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02367Substrates
    • H01L21/02428Structure
    • H01L21/0243Surface structure
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02367Substrates
    • H01L21/02433Crystal orientation
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02436Intermediate layers between substrates and deposited layers
    • H01L21/02439Materials
    • H01L21/02455Group 13/15 materials
    • H01L21/02458Nitrides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02436Intermediate layers between substrates and deposited layers
    • H01L21/02494Structure
    • H01L21/02496Layer structure
    • H01L21/0251Graded layers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02518Deposited layers
    • H01L21/02521Materials
    • H01L21/02538Group 13/15 materials
    • H01L21/0254Nitrides
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10HINORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80Constructional details
    • H10H20/81Bodies
    • H10H20/813Bodies having a plurality of light-emitting regions, e.g. multi-junction LEDs or light-emitting devices having photoluminescent regions within the bodies
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10HINORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80Constructional details
    • H10H20/81Bodies
    • H10H20/815Bodies having stress relaxation structures, e.g. buffer layers

Definitions

  • the technology disclosed herein relates generally to lattice-mismatched semiconductor heterostructures, in particular pseudomorphic layers having a thickness greater than the critical thickness predicted therefor.
  • the lattice parameter in the c-plane of GaN is approximately 2.4% larger than that of AlN.
  • the initial layer typically grows pseudomorphically — that is, the epitaxial layer will be compressed (experience compressive strain) in the plane of the substrate surface if the intrinsic lattice parameter of the substrate is smaller than that of the epitaxial layer.
  • the epitaxial layer will be stretched or put under tensile strain when the intrinsic lattice parameter of the epitaxial layer is smaller than that of the substrate.
  • the strain energy in the epitaxial layer will grow and, typically, the layer will find some way to reduce the strain energy. This may occur by plastic flow through the motion of dislocations, through the creation of surface mo ⁇ hological features which allow strain relaxation, or, particularly when the strain is tensile, through cracking of the film.
  • Pseudomorphic layers are attractive for at least two reasons.
  • the first is that when an epitaxial layer is grown on a low-dislocation substrate, the pseudomorphic epitaxial layer may also be grown with very low dislocation densities, often with the same dislocation density as the substrate.
  • the second advantage accrues from the ability to tailor the band structure through the large resulting biaxial strains. For example, the strain can be used to break the degeneracy between heavy and light carrier bands and, as a result, obtain higher carrier mobilities.
  • a technique is provided for growing very thick pseudomorphic films of alloys of AlN, GaN, and InN on high-quality AlN substrates.
  • a pseudomorphic film is one where the strain parallel to the interface is approximately that needed to distort the lattice in the film to match that of the substrate.
  • the parallel strain in a pseudomorphic film will be nearly or approximately equal to the difference in lattice parameters between an unstrained substrate parallel to the interface and an unstrained epitaxial layer parallel to the interface.
  • very thick refers to a thickness of the epitaxial layer that substantially exceeds (by a factor of at least 5 for substantially In-free layers or by a factor of at least 10 for layers including In) the expected critical thickness for the epitaxial film based on standard calculations of the thickness where strain relaxation should start to occur through the nucleation and/or motion of threading dislocations (or energy equilibrium calculations).
  • the expected critical thickness may be calculated as described in, e.g., Matthews and Blakeslee, J. Crystal Growth 27, 1 18 (1974), and/or U.S. Patent No. 4,088,515, the entire disclosure of each being hereby incorporated by reference.
  • embodiments of the invention feature a semiconductor heterostructure including an aluminum nitride single-crystal substrate and at least one strained layer epitaxially grown thereover.
  • the strained layer includes at least one of AlN, GaN, InN, or any binary or tertiary alloy combination thereof.
  • the thickness of the strained layer exceeds the predicted critical thickness associated therewith by at least a factor of 5, or even by at least a factor of 10.
  • the strained layer may be substantially In-free and/or have a density of macroscopic defects less than approximately 1 mm "2 . In an embodiment, the density of macroscopic defects is approximately 0 mm '2 .
  • Embodiments of the invention may include one or more of the following.
  • the strain parallel to the strained layer is greater than 80% of a difference between the parallel lattice parameters of an unstrained alloy of the same composition as the strained layer and the relaxed platform disposed beneath the strained layer.
  • the strain parallel to the strained layer may even be approximately 95% - 100% of this difference.
  • the relaxed platform may be either the substrate or a relaxed semiconductor layer formed between the substrate and the strained layer.
  • the strained layer may include Al x Gai -x N, have a thickness greater than approximately 200 nm, and have an Al content x less than approximately 0.65.
  • the thickness of the strained layer may be greater than approximately 1 ⁇ m, and the average threading dislocation density of the strained layer may be less than approximately 10,000 cm "2 .
  • the predicted critical thickness may be calculated with the Matthews-Blakeslee theory.
  • embodiments of the invention feature a method of forming a semiconductor structure including providing an aluminum nitride single-crystal substrate and epitaxially depositing thereover a strained layer.
  • the strained layer includes at least one of AlN, GaN, InN, or any binary or tertiary alloy combination thereof.
  • the thickness of the strained layer exceeds the predicted critical thickness associated therewith by at least a factor of 5, or even by at least a factor of 10.
  • the strained layer may be substantially In- free and/or have a density of macroscopic defects less than approximately 1 mm "2 . In an embodiment, the density of macroscopic defects is approximately 0 mm "2 .
  • Embodiments of the invention may include one or more of the following.
  • a buffer- layer may be formed over the substrate prior to depositing the strained layer, and a graded layer may be formed between the buffer layer and the strained layer.
  • the strained layer may include AlGaN, and depositing the strained layer may include introducing trimethylaluminum and trimethylgallium into a reactor.
  • the initial flow rate of trimethylgallium during the deposition of the strained layer may be lower than a final trimethylgallium flow rate.
  • the predicted critical thickness may be calculated with the Matthews-Blakeslee theory.
  • the aluminum nitride single-crystal substrate may have an RMS surface roughness less than approximately 0.5 nm for a 10 ⁇ m x lO ⁇ m area, a surface misorientation between approximately 0.3° and 4°, and a threading dislocation density less than approximately 10 4 cm '2 .
  • the density of the strained layer may be approximately equal to the threading dislocation density of the aluminum nitride single-crystal substrate.
  • embodiments of the invention feature a device selected from the group consisting of a field effect transistor, a light-emitting diode, and a laser diode, the device including at least a portion of the strained heterostructure described above.
  • the device may be a light-emitting diode having at least one interdigitated contact.
  • embodiments of the invention feature a device selected from the group consisting of a field effect transistor, a light-emitting diode, and a laser diode, the device including at least a portion of a strained heterostructure.
  • the strained heterostructure includes an aluminum nitride single-crystal substrate and a plurality of strained layers epitaxially grown thereover.
  • Each of the plurality of the strained layers includes at least one of AlN, GaN, InN, or any binary or tertiary alloy combination thereof.
  • the total thickness of the plurality of strained layers exceeds the predicted critical thickness associated therewith by at least a factor of 5, or even by at least a factor of 10.
  • the lattice parameter parallel to the surface of the aluminum nitride single-crystal substrate of each of the plurality of strained layers may be different from the lattice parameter of the aluminum nitride single-crystal substrate by less than 0.2%.
  • One or more of the plurality of strained layers may be In- free.
  • Fig. 1 is a graph of predicted critical thickness and pseudomorphic strain for Al x Ga ⁇ -x N layers of various Al contents x formed on AlN substrates;
  • Fig. 2 is a schematic depicting a pseudomorphic strained layer formed on a substrate
  • Fig. 3 is a schematic of a pseudomorphic strained layer-based device structure
  • Figs. 4A and 4B are schematics of processed devices utilizing the layer structure of Fig. 3.
  • the predicted critical thickness calculated in accordance with the Matthews- Blakeslee theory as a function of Al concentration in Al x Gai - ⁇ N layer growth on a c-face AlN substrate, is shown in Fig. 1. Also shown is the pseudomorphic strain of the Al x Ga
  • . X N layers attained in the absence of relaxation. Unexpectedly, we have found that it is possible to grow pseudomorphic layers with thicknesses much greater than the predicted critical thickness. For example, the critical thickness of an Al x Ga) -X N layer with x 0.6 is about 40 nanometers (nm), as shown in Fig. 1.
  • the term "high quality” refers to epitaxial layers having a threading dislocation density of approximately 10 6 cm “2 or less. In certain embodiments, high-quality layers have threading dislocation densities of approximately 10 4 cm “ 2 or less, or even approximately 10 2 cm '2 or less.
  • the term "pseudomorphic” is utilized herein to refer to epitaxial layers strained to at least approximately 80% of a lattice parameter of an underlying substrate (i.e., less than approximately 20% relaxed to its innate lattice parameter).
  • a pseudomorphic layer may be approximately fully strained to the lattice parameter of the underlying substrate.
  • the term "mirror smooth” refers to layer root-mean- squared ("RMS") surface roughnesses less than approximately 5 nm in a 5 ⁇ m x 5 ⁇ m area (as measured by an atomic-force microscope). In preferred embodiments the RMS surface roughness is less than approximately 1 nm in a 5 ⁇ m x 5 ⁇ m area.
  • a thick pseudomorphic semiconductor layer fabricated in accordance herewith is shown in Fig. 2.
  • a semiconductor substrate 200 is provided.
  • semiconductor substrate 200 includes or consists essentially of AlN.
  • the top surface 210 of semiconductor substrate 200 may be prepared for epitaxial growth by at least one of planarization (e.g., by chemical-mechanical polishing) or cleaning prior to deposition of one or more epitaxial layers thereon.
  • a strained epitaxial layer 220 is then deposited on semiconductor substrate 200, e.g., by organometallic vapor-phase epitaxy, to a thickness exceeding its predicted critical thickness. As can be seen in Fig. 1 , the predicted critical thickness of an exemplary epitaxial layer 220 consisting of Al x Ga).
  • X N grown on a semiconductor substrate 200 consisting of AlN depends on the Al content x.
  • the thickness of epitaxial layer 220 exceeds its predicted critical thickness by at least a factor of 5, or even by at least a factor of 10, and epitaxial layer 220 remains pseudomorphic.
  • the thickness of epitaxial layer 220 may even exceed its predicted critical thickness by a factor of 20 or more.
  • epitaxial layer 220 may actually consist of a plurality of discrete layers, each one pseudomorphically strained to the lattice parameter of semiconductor substrate 200.
  • the plurality of layers may include layers with graded composition, e.g., layers including AlN, InN, and/or GaN in which the concentration of one or more of the group III atoms changes with thickness. Such layers may be graded in discrete steps or linearly in composition.
  • Strained epitaxial layer 220 may also be deposited on an optional relaxed semiconductor layer (not shown) formed over semiconductor substrate 200. In this case, the strain in epitaxial layer 220 and the predicted critical thickness therefor will be a function of the lattice parameter of the relaxed semiconductor layer rather than that of semiconductor substrate 200.
  • Epitaxial layer 220 remains pseudomorphic, and the thickness of epitaxial layer 220 exceeds this predicted critical thickness by at least a factor of 5. In certain embodiments, the thickness of epitaxial layer 220 exceeds this predicted critical thickness by at least a factor of 10 or even at least a factor of 20. Thus, either semiconductor substrate 200 or the optional relaxed semiconductor layer can act as a relaxed "platform" to which epitaxial layer 220 is strained.
  • TDD threading dislocation density
  • Defects at the surface of the semiconductor substrate 200 may also cause roughening of epitaxial layer 220. Once roughening occurs, strain relaxation occurs at the sidewalls of terraces and islands on the epitaxial surface. When these terraces and islands coalesce, they may deleteriously form high densities of threading dislocations at the coalescence boundaries.
  • step-flow growth during the epitaxial deposition aids the prevention of relaxation, and the proper conditions for step-flow growth depend on the substrate orientation of the semiconductor substrate 200.
  • substrates are very closely oriented to on-axis (i.e., the surface normal of the substrate is very closely aligned to a major crystallographic axis)
  • the density of steps across the surface of the substrate is low.
  • incoming Al, Ga, or In atoms must diffusive relatively large distances to incorporate into the growing epitaxial layer at a step edge, i.e., maintain step-flow growth.
  • step-flow growth may be maintained by (i) enhancing the long-distance diffusion of incoming atoms of the growth species and/or (ii) reducing the diffusion distance required to reach a step edge (i.e., increase the step density on the surface).
  • Such long-distance diffusion may be enhanced by performing the epitaxial growth at higher temperatures (i.e., up to approximately 1 100 0 C) or, in the case of In-free, high Al content (e.g., greater than approximately 50% Al content), by increasing the growth temperature to a range of greater than approximately 1 100 0 C to approximately 1300 0 C.
  • long-distance diffusion may also be enhanced by decreasing the ratio of the nitrogen species (i.e., the group V species) in the epitaxial reactor in comparison to the group III species.
  • a V-III ratio beneficial for enhancing long-distance diffusion of the growth species is less than approximately 1,000, and may even be less than approximately 10.
  • the density of step edges on semiconductor substrate 200 may also be increased (thus reducing the required diffusion distances required to reach a step) by increasing the misorientation between the major crystallographic axis and the surface normal of the substrate. In an embodiment, the misorientation of semiconductor substrate 200 is approximately 1°.
  • Kinetic barriers to strain relaxation may also be beneficially utilized to produce thick pseudomorphic epitaxial layers. Since any alloy of AlN, GaN, and InN (with nonzero content of either GaN or InN) will have a larger relaxed lattice parameter than an underlying AlN substrate, these epitaxial films will typically not relax by cracking. Relaxation may occur by the formation of misfit dislocations which run parallel to the interface between the AlN substrate and epitaxial alloy layer. These misfit dislocations may either result from the motion of existing threading dislocations which propagate into epitaxial layer 220 from semiconductor substrate 200, or from new dislocation loops forming either from the surface or from some macroscopic defect on the surface of substrate 200.
  • semiconductor substrate 200 has a threading dislocation density less than approximately 10 6 cm '2 . In other embodiments, semiconductor substrate 200 has a threading dislocation density less than approximately 10 cm '2 or even less than approximately 10 2 cm "2 . Semiconductor substrate 200 may also have a density of particulate surface defects less than approximately 100 cm "2 . Utilization of such optimized semiconductor substrates minimizes or eliminates glide of existing dislocations and dislocation nucleation at surface defects as relaxation mechanisms.
  • the remaining relaxation mechanism surface nucleation of dislocation loops — occurs only at strain energies sufficiently high to facilitate fabrication of thick pseudomorphic epitaxial layers. Therefore, the fabrication of thick strained epitaxial layer 220 having a thickness greater than its predicted critical thickness by at least approximately a factor of 5 is facilitated. Moreover, since In may have the additional effect of hindering dislocation motion and concomitant relaxation, a strained epitaxial layer 220 containing In may achieve a pseudomorphic thickness greater than its predicted critical thickness by at least approximately a factor of 10.
  • certain crystallographic orientations of semiconductor substrate 200 may be particularly favorable in the fabrication of thick epitaxial layers of highly strained alloys.
  • Liu et al. point out, the main slip system of the wurzite crystal structure of GaN and its alloys is ⁇ 1 1.2> ⁇ 00.2 ⁇ . ⁇ See R. Liu, J. Mei, S. Srinivasan, H. Omiya, F.A. Ponce, D.
  • the misorientation of semiconductor substrate 200 is greater than 0° but is less than approximately 4°.
  • a large c-face AlN substrate with low dislocation density (roughly 5 x 10 3 cm '2 ) was prepared as described in the '660 application. The miscut of this substrate was approximately 1°.
  • the Al-polarity surface of the c-face AlN substrate — the (0001) face — was prepared as described in U.S. Patent No. 7,037,838 ("the '838 patent”), the entire disclosure of which is hereby incorporated by reference.
  • TMA trimethylaluminum
  • x N was then grown by switching in trimethylgallium (“TMG”) with ramping up TMG and ramping down the TMA gas flow to reach the target Al% over a 15 minute interval to grow approximately 0.1 ⁇ m of linearly graded alloy.
  • the TMA and TMG flows were kept constant and a final layer of -63% Al concentration and approximately 0.6 ⁇ m thickness was grown with an approximate growth rate of 1.0 ⁇ m/hr.
  • the chamber pressure was maintained at -25 to 100 mbar.
  • the V-III ratio was maintained between 500 and 2,000 during the growth sequence.
  • the parallel strain i.e., strain in the plane of the substrate was measured to be slightly greater than 0.8% and represented pseudomorphic growth even though the layer exceeded the predicted critical thickness by more than an order of magnitude.
  • the double-crystal ⁇ rocking curve widths about the (00.2) and the (10.2) reflections (measured with a Philip X' Pert system) for the Al x Ga ⁇ -x N layer were 50 arcsec and 60 arcsec, respectively.
  • the strain parallel to the interface was measured to be nearly 1% and the epitaxial layer was pseudomorphic to the underlying AlN substrate.
  • Etch pit densities were measured using a molten KOH etch to determine the density of threading dislocations in the Al x Ga I -X N epitaxial layer. The measured densities were in the range of 0.8 - 3 x 10 5 cm '2 .
  • the substrate was heated to approximately 1 100 °C under a flowing hydrogen and ammonia gas mixture.
  • TMA was then introduced and a 0.4 ⁇ m-thick AlN buffer layer was grown on the substrate at an approximate growth rate of 0.4 ⁇ m/hr.
  • a graded layer Al x GaJ. X N was then grown by switching in TMG with ramping up TMG while maintaining TMA gas flow to reach the target Al% over a 6-minute interval to grow approximately 0.05 ⁇ m of linearly graded alloy. After this transition layer, the TMA and TMG flows are kept constant and a final layer of -58% Al concentration and approximately 0.5 ⁇ m thickness was grown with an approximate growth rate of 0.8 ⁇ m/hr.
  • the chamber pressure was maintained at approximately 20 Torr.
  • the V-III ratio was maintained between 900 and 3,200 during growth sequence.
  • the parallel strain was measured to be slightly greater than 1.0% and represented pseudomorphic growth even though the layer exceeded the predicted critical thickness by more than an order of magnitude.
  • the threading dislocation density therein may be approximately equal to the threading dislocation density of semiconductor substrate 200.
  • substrates from AlN boules grown by the techniques described in the '660 application may have very low dislocation densities — under 10,000 cm “2 , typically about 1,000 cm “2 , and, in certain embodiments, under 500 cm “2 and even under 100 cm “2 — that are "inherited" by pseudomorphic epitaxial layers grown thereon.
  • the threading dislocation density of epitaxial layer 200 may be greater than that of semiconductor substrate 200 by no more than approximately a factor of 10.
  • strained epitaxial layer 220 is substantially free of local elastic strain relaxation caused by the formation of, e.g., macroscopic defects such as islands and pinholes (further described below). Moreover, the strain in epitaxial layer 220 may be approximately completely a result of lattice mismatch to substrate 200. For example, epitaxial layer 220 will be approximately free of strain due to thermal expansion mismatch with substrate 200.
  • polarization effects in epitaxial layer 220 may affect device performance.
  • top surface 210 which is non-polar (e.g., the a- or m-plane of a substrate 200 consisting of AlN)
  • polarization effects in the layer are minimized.
  • pseudomorphic structures grown on the c-plane along the [0001] direction may have strong polarization effects which influence the charge distribution within the device.
  • the polarization charge at the channel/barrier interface is carefully increased to counteract backside depletion effects associated with the AlN/GaN hetero-interface transitioning from the AlN buffer structure.
  • the electrical efficiency ⁇ ⁇ (defined as photon energy divided by the product of the applied voltage and electron charge, i.e., /z ⁇ /eV), represents the amount of electrical energy converted to photon energy.
  • the applied forward voltage is determined by the diode characteristics, and should be as low as possible in order to get the maximum current (and hence maximize the number of electrons eligible to convert to photons) for a given input power.
  • the IQE is the ratio of the photons created in the active region of the semiconductor chip to the number of electrons injected into the LED.
  • a pseudomorphic UV light emitting diode (“PUVLED”) structure 300 is formed.
  • a semiconductor substrate 305 which includes or consists essentially of one or more semiconductor materials, is provided.
  • semiconductor substrate 305 includes or consists essentially of a Ill-nitride semiconductor material, e.g., AlN.
  • Semiconductor substrate 305 may be miscut such that the angle between its c-axis and its surface normal is between 0.3° and 4°. In a preferred embodiment, the misorientation of the surface of semiconductor substrate 305 is approximately 1°.
  • the surface of semiconductor substrate 305 may have an Al- or N-polarity, and may be planarized, e.g., by chemical- mechanical polishing.
  • the surface of semiconductor substrate 305 is prepared as disclosed in the '838 patent.
  • the RMS surface roughness of semiconductor substrate is preferably less than approximately 0.5 nm for a 10 ⁇ m x 10 ⁇ m area.
  • atomic-level steps are detectable on the surface when probed with an atomic- force microscope.
  • the threading dislocation density of semiconductor substrate 305 may be measured using, e.g., etch pit density measurements after a 5 minute KOH-NaOH eutectic etch at 450 °C.
  • the threading dislocation density is less than approximately 2 x 10 3 cm '2 .
  • substrate 305 has an even lower threading dislocation density, as described above in reference to semiconductor substrate 200.
  • Semiconductor substrate 305 may be topped with a homoepitaxial layer (not shown) that includes or consists essentially of the same semiconductor material present in semiconductor substrate 300, e.g., AlN.
  • a graded buffer layer 310 is formed on semiconductor substrate 305.
  • Graded buffer layer 310 may include or consist essentially of one or more semiconductor materials, e.g., Al x Ga ⁇ -x N.
  • graded buffer layer 310 has a composition approximately equal to that of semiconductor substrate 305 at an interface therewith in order to promote two-dimensional growth and avoid deleterious islanding (such islanding may result in undesired elastic strain relief in graded buffer layer 310 and subsequently grown layers).
  • graded buffer layer 310 at an interface with subsequently grown layers is generally chosen to be close to that of the desired active region of the device (e.g., the Al x Gai -x N concentration that will result in the desired wavelength emission from the PUVLED).
  • graded buffer layer 310 includes Al x Gai. x N graded from an Al concentration x of approximately 100% to an Al concentration x of approximately 60%.
  • a bottom contact layer 320 is subsequently formed above graded layer 310, and may include or consist essentially of Al x Ga ⁇ -x N doped with at least one impurity, e.g., Si.
  • the Al concentration x in bottom contact layer 320 is approximately equal to the final Al concentration x in graded layer 310.
  • Bottom contact layer 320 may have a thickness sufficient to prevent current crowding after device fabrication (as described below) and/or to stop on during etching to fabricate contacts.
  • the thickness of bottom contact layer 320 may be less than approximately 200 nm.
  • the final PUVLED may be fabricated with back-side contacts, as described below in reference to Fig. 4B.
  • bottom contact layer 320 will have high electrical conductivity even with a small thickness due to the low defect density maintained when the layer is pseudomorphic.
  • a multiple-quantum well (“MQW”) layer 330 is fabricated above bottom contact layer 320.
  • MQW layer 330 corresponds to the "active region" of PUVLED structure 300 and includes a plurality of quantum wells, each of which may include or consist essentially of AlGaN.
  • each period of MQW layer 330 includes an Al x Ga].
  • the difference between x and y is large enough to obtain good confinement of the electrons and holes in the active region, thus enabling high ratio of radiative recombination to non-radiative recombination.
  • the difference between x and y is approximately 0.05, e.g., x is approximately 0.35 and y is approximately 0.4.
  • MQW layer 330 may include a plurality of such periods, and may have a total thickness less than approximately 50 nm.
  • MQW layer 330 may be formed an optional thin electron-blocking (or hole-blocking if the n-type contact is put on top of the device) layer 340, which includes or consists essentially of, e.g., Al x Gai -x N, which may be doped with one or more impurities such as Mg.
  • Electron-blocking layer 340 has a thickness of, e.g., approximately 20 nm.
  • a top contact layer 350 is formed above electron blocking layer 340, and includes or consists essentially of one or more semiconductor materials, e.g., Al x Gai -x N, doped with at least one impurity such as Mg.
  • Top contact layer 350 is doped either n-type or p-type, but with conductivity opposite that of bottom contact layer 310.
  • the thickness of top contact layer 350 is, e.g., between approximately 50 nm and approximately 100 nm.
  • Top contact layer 350 is capped with a cap layer 360, which includes or consists essentially of one or more semiconductor materials doped with the same conductivity as top contact layer 350.
  • cap layer 360 includes GaN doped with Mg, and has a thickness between approximately 10 nm and approximately 200 nm, preferably approximately 50 nm.
  • high-quality ohmic contacts may be made directly to top contact layer 350 and cap layer 360 is omitted.
  • layers 310 - 350 are all pseudomorphic, cap layer 360 may relax without introducing deleterious defects into the active layers below which would adversely affect the performance of PUVLED structure 300.
  • etching and final contact formation completes the formation of PUVLED structure 300.
  • Each of layers 310 - 350 is pseudomorphic, and each layer individually may have a thickness greater than its predicted critical thickness, as described above.
  • the collective layer structure including layers 310 - 350 may have a total thickness greater than the predicted critical thickness for the layers considered collectively (i.e., for a multiple-layer structure, the entire structure has a predicted critical thickness even when each individual layer would be less than a predicted critical thickness thereof considered in isolation).
  • PUVLED structure 300 (and/or strained epitaxial layer 220 described above) are formed substantially free (i.e., having less than approximately 1 mm " 2 , or even approximately 0 mm "2 ) of macroscopic defects such as pinholes, mounds, or "V pits.” Such defects are often observed in the growth of, e.g., strained InGaN layers on GaN substrates with high dislocation densities. (See T.L. Song, J. Appl. Phys. 98, 084906 (2005), the entire content of which is hereby incorporated by reference).
  • Macroscopic defects may cause local relaxation of the strain in the pseudomorphic layer(s), deleteriously affect devices fabricated from the epitaxial layers due to disruptions of the quantum well structures and/or shorting of the p- and n-type contacts, or increase the surface roughness of the layers.
  • Macroscopic defect- free PUVLED structure 300 may advantageously be utilized in the fabrication of PUVLEDs sized greater than approximately 0.1 mm x approximately 0.1 mm. [0034] PUVLED structure 300 has an emission wavelength in the range of approximately 210 nm to approximately 320 nm, e.g., approximately 280 nm.
  • the threading dislocation density in the layers is less than approximately 10 5 cm "2 , and may be approximately equal to the threading dislocation density in substrate 305.
  • PUVLED structure 300 has a wall-plug efficiency (i.e., total optical power out divided by total electrical power in) greater than approximately 10% (or even greater than approximately 20% in some embodiments) and/or a lifetime greater than approximately 10,000 hours.
  • Laser diode (LD) structures may also benefit from a pseudomorphic structure.
  • a preferred LD structure will be similar to that of PUVLED structure 300, with the addition of layers which properly confine photons to create a resonant cavity.
  • the resonant cavity will be directed perpendicular to the growth direction and mirrors will be created by cleaving or etching the semiconductor layer structure.
  • layer 320 below the MQW layer 330 and layers 340 and 350 above the MQW will need to be modified to act as effective cladding layers to ensure that the emitted photons effectively propagate perpendicular to layer growth direction without significant absorption.
  • a vertical cavity surface-emitting laser VCSEL
  • layers 320, 340, and 350 may be replaced with multilayer structures that will act as mirrors (e.g., Bragg reflectors) to create a photon cavity that will direct photons along the growth direction of the semiconductor layers.
  • a semiconductor LD fabricated with nitride semiconductors may have an emission wavelength shorter than approximately 300 nm, and, in some embodiments, shorter than approximately 280 nm.
  • PUVLED 400 is formed by etching, e.g., plasma etching, through the layer sequence in PUVLED structure 300 and stopping on or in bottom contact layer 310.
  • Contacts 410, 420 are formed on bottom contact layer 310 and on cap layer 360, respectively.
  • Contacts 410, 420 are formed of a conductive material, e.g., a metal such as Ni/Au alloy (typically used for p-type contacts) or a Ti/Al/Ti/Au stack (typically used for n- type contacts), and may be formed by, e.g., sputtering or evaporation.
  • Contacts 410, 420 may include or consist essentially of the same or different conductive materials (such that optimal contact is made to the oppositely doped bottom contact layer 310 and cap layer 360).
  • Contact 420 may also include an ultraviolet ("UV") reflector.
  • the UV reflector is designed to improve the extraction efficiency of photons created in the active region of the device by redirecting photons which are emitted toward contact 420 (where they cannot escape from the semiconductor layer structure) and redirecting them toward a desired emission surface, e.g., the bottom surface of PUVLEDs 400, 450.
  • contact 420 is also formed above cap layer 360.
  • contact 410 (which may be a plurality of separate contacts), is formed on the backside of the PUVLED active layer structure.
  • substrate 305 is optionally thinned to approximately 150 ⁇ m by, e.g., mechanical grinding or polishing.
  • a mask layer (not shown), formed of, e.g., Ni, is formed on the backside of substrate 305 and patterned by standard photolithography.
  • the exposed regions of substrate 305 are etched by, e.g., plasma or wet etching, and the etch is stopped on or in bottom contact layer 310. Etch stopping on bottom contact layer 310 is facilitated by detection of Ga in the plasma etcher as substrate 305 will be pure AlN in many embodiments.
  • Contact 410 is then formed on the exposed portions of bottom contact layer 310. Contact 410 may be interdigitated to maximize the light output from PUVLED 450.
  • the tapered structures created on the backside of substrate 305 will help gather photons from a much larger emission angle from the MQW structure in layer 340 and direct them out the emission surface near the tips of the taped features shown on the etched backside of the substrate 305 shown in Fig. 4B.
  • This will substantially improve the photon extraction efficiency of the PUVLED since, without the tapered structures, only a small fraction of the photons directed toward a flat emission surface (such as that shown in Fig. 4A) will fall with the critical acceptance cone for emission due to the large index of refraction for these semiconductor materials.

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