WO2010112980A1 - Iii-nitride light emitting device including porous semiconductor layer - Google Patents

Iii-nitride light emitting device including porous semiconductor layer Download PDF

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Publication number
WO2010112980A1
WO2010112980A1 PCT/IB2009/051400 IB2009051400W WO2010112980A1 WO 2010112980 A1 WO2010112980 A1 WO 2010112980A1 IB 2009051400 W IB2009051400 W IB 2009051400W WO 2010112980 A1 WO2010112980 A1 WO 2010112980A1
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region
layer
porous
nitride
ill
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Jr. Jonathan J. Wierer
John E. Epler
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Koninklijke Philips NV
Lumileds LLC
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Koninklijke Philips Electronics NV
Philips Lumileds Lighing Co LLC
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/81—Bodies
    • H10H20/817—Bodies characterised by the crystal structures or orientations, e.g. polycrystalline, amorphous or porous
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/81—Bodies
    • H10H20/815—Bodies having stress relaxation structures, e.g. buffer layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/27—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using selective deposition, e.g. simultaneous growth of monocrystalline and non-monocrystalline semiconductor materials
    • H10P14/271—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using selective deposition, e.g. simultaneous growth of monocrystalline and non-monocrystalline semiconductor materials characterised by the preparation of substrate for selective deposition
    • H10P14/272—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using selective deposition, e.g. simultaneous growth of monocrystalline and non-monocrystalline semiconductor materials characterised by the preparation of substrate for selective deposition using mask materials other than SiO2 or SiN
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/29—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials characterised by the substrates
    • H10P14/2901—Materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/32—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials characterised by intermediate layers between substrates and deposited layers
    • H10P14/3202—Materials thereof
    • H10P14/3214—Materials thereof being Group IIIA-VA semiconductors
    • H10P14/3216—Nitrides
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/32—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials characterised by intermediate layers between substrates and deposited layers
    • H10P14/3242—Structure
    • H10P14/3256—Microstructure
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/34—Deposited materials, e.g. layers
    • H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
    • H10P14/3414—Deposited materials, e.g. layers characterised by the chemical composition being group IIIA-VIA materials
    • H10P14/3416—Nitrides
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/01—Manufacture or treatment
    • H10H20/011—Manufacture or treatment of bodies, e.g. forming semiconductor layers
    • H10H20/013—Manufacture or treatment of bodies, e.g. forming semiconductor layers having light-emitting regions comprising only Group III-V materials
    • H10H20/0133—Manufacture or treatment of bodies, e.g. forming semiconductor layers having light-emitting regions comprising only Group III-V materials with a substrate not being Group III-V materials
    • H10H20/01335—Manufacture or treatment of bodies, e.g. forming semiconductor layers having light-emitting regions comprising only Group III-V materials with a substrate not being Group III-V materials the light-emitting regions comprising nitride materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/81—Bodies
    • H10H20/822—Materials of the light-emitting regions
    • H10H20/824—Materials of the light-emitting regions comprising only Group III-V materials, e.g. GaP
    • H10H20/825—Materials of the light-emitting regions comprising only Group III-V materials, e.g. GaP containing nitrogen, e.g. GaN

Definitions

  • the present invention relates to a Ill-nitride light emitting device including a porous layer.
  • LEDs light emitting diodes
  • RCLEDs resonant cavity light emitting diodes
  • VCSELs vertical cavity laser diodes
  • edge emitting lasers are among the most efficient light sources currently available.
  • Materials systems currently of interest in the manufacture of high-brightness light emitting devices capable of operation across the visible spectrum include Group III -V semiconductors, particularly binary, ternary, and quaternary alloys of gallium, aluminum, indium, and nitrogen, also referred to as Ill-nitride materials.
  • Ill-nitride light emitting devices are fabricated by epitaxially growing a stack of semiconductor layers of different compositions and dopant concentrations on a sapphire, silicon carbide, Ill-nitride, or other suitable substrate by metal-organic chemical vapor deposition (MOCVD), molecular beam epitaxy (MBE), or other epitaxial techniques.
  • MOCVD metal-organic chemical vapor deposition
  • MBE molecular beam epitaxy
  • the stack often includes one or more n-type layers doped with, for example, Si, formed over the substrate, one or more light emitting layers in an active region formed over the n-type layer or layers, and one or more p-type layers doped with, for example, Mg, formed over the active region. Electrical contacts are formed on the n- and p-type regions.
  • a semiconductor structure comprising a Ill-nitride light emitting layer disposed between an n-type region and a p-type region is grown over a porous Ill-nitride region.
  • a III -nitride layer comprising InN is disposed between the light emitting layer and the porous Ill-nitride region. Since the III- nitride layer comprising InN is grown on the porous region, the Ill-nitride layer comprising InN may be at least partially relaxed, i.e. the Ill-nitride layer comprising InN may have an in- plane lattice constant larger than an in-plane lattice constant of a conventional GaN layer grown on sapphire.
  • Fig. 1 is a cross sectional view of a III -nitride layer grown over a substrate.
  • Fig. 2 is a cross sectional view of a porous region formed in a Ill-nitride layer.
  • Fig. 3 is a cross sectional view of a relaxed Ill-nitride layer grown over a porous region.
  • Fig. 4 is a cross sectional view of a device structure grown over a relaxed III- nitride layer.
  • Fig. 5 is a cross sectional view of a mask formed on a Ill-nitride layer grown over a substrate.
  • Fig. 6 is a cross sectional view of porous regions formed through openings in a mask.
  • Fig. 7 is a cross sectional view of a relaxed Ill-nitride layer grown over the porous regions and the mask.
  • Fig. 8 is a cross sectional view of a portion of a Ill-nitride device mounted in flip chip configuration on a mount.
  • Fig. 9 is an exploded view of a packaged light emitting device.
  • Fig. 10 is a plot of bandgap as a function of lattice constant for InGaN, AlGaN and AlInN alloys.
  • the performance of a semiconductor light emitting device may be gauged by measuring the external quantum efficiency, which measures the number of photons extracted from the device per electron supplied to the device.
  • the external quantum efficiency is the product of the internal quantum efficiency, defined as the number of photons produced per electron supplied to the device, and the extraction efficiency.
  • the external quantum efficiency may be dominated by the internal quantum efficiency. For simplicity, radiative processes, non-radiative processes, and injection efficiency are all included in the internal quantum efficiency.
  • the internal quantum efficiency of the device initially increases, then decreases. As the current density increases past zero, the internal quantum efficiency increases, reaching a peak at a given current density (for example, at about 10 A/cm for some devices). As current density increases beyond the peak, the internal quantum efficiency initially drops quickly, then the decrease slows at higher current density (for example, beyond 200 A/cm for some devices).
  • the internal quantum efficiency of a device also decreases as the InN composition in the light emitting region increases, which is required for longer wavelength devices in the Ill-nitride system.
  • Ill-nitride devices are often grown on sapphire (AI 2 O3) or SiC substrates.
  • Ill-nitride devices often include GaN, InGaN, and AlGaN layers.
  • InGaN light emitting layers are often grown over GaN.
  • the strain in the light emitting layers may permit, for a given efficiency, growth of thicker light emitting layers and/or higher InN composition light emitting layers.
  • an "in-plane” lattice constant refers to the actual lattice constant of a layer within the device
  • a “bulk” lattice constant refers to the lattice constant of relaxed, free-standing material of a given composition.
  • strain, ⁇ , in Eq. (1) can be either positive or negative, i.e., ⁇ > 0 or ⁇ ⁇ 0.
  • tensile strain include a strained AlGaN film grown over unstrained GaN, or a strained GaN film grown over unstrained InGaN.
  • the strained film has a bulk lattice constant that is smaller than the bulk lattice constant of the unstrained layer on which it is grown, so the in-plane lattice constant of the strained film is stretched to match that of the unstrained layer, giving ⁇ > 0 in Eq. (1).
  • compressive strain include a strained InGaN film grown over unstrained GaN, or a strained GaN film grown over unstrained AlGaN.
  • the strained film has a bulk lattice constant that is larger than the bulk lattice constant of the unstrained layer on which it is grown, so the in-plane lattice constant of the strained film is compressed to match that of the unstrained layer, giving ⁇ ⁇ 0 in Eq. (1).
  • the strain pulls the atoms apart from one another in order to increase the in-plane lattice constant.
  • Tensile strain is often undesirable, because the film can respond to the tensile strain by cracking, which decreases the strain in the film, but compromises the structural and electrical integrity of the film.
  • the strain pushes the atoms together. This effect can reduce the incorporation of large atoms such as indium in an InGaN film, for example, or can negatively impact the material quality of the InGaN light emitting layer in an InGaN LED.
  • strain shall be understood to mean the absolute value, or magnitude of the strain, as defined in Eq. (2).
  • a porous semiconductor region is included in a Ill-nitride light emitting device.
  • the porous region may reduce the strain in layers grown over the porous region, particularly in the light emitting layer.
  • Figs. 1-4 illustrate a first embodiment of a device including a porous region.
  • a Ill-nitride layer 12 is grown over a suitable growth substrate 10.
  • III- nitride layer 12 is generally an n-type GaN layer that is not intentionally doped, though it may be an intentionally doped layer (generally n-type), and it may be a binary Ill-nitride material other than GaN, or a ternary or quarternary material such as InGaN, AlGaN, or AlInGaN.
  • Substrate 10 may be, for example, GaN, sapphire, SiC, or a compound substrate such as SiC on Si or SiC on an insulator.
  • layer 12 is made porous. Porous region 16 may be in contact with substrate 10, or may be separated from substrate 10 by a non- porous remaining portion 14 of Ill-nitride layer 12. In embodiments where a sapphire substrate is later removed by laser lift off, the entire thickness of layer 12 may be made porous such that porous material is in direct contact with substrate 10. Porous material at the interface with substrate 10 may reduce the laser power necessary for lift off and thereby reduce the amount of damage to the Ill-nitride material caused by the laser lift off process.
  • layer 12 may be made porous as follows: a platinum wire connected to layer 12 serves as the anode. The other end of the platinum wire serves as the cathode.
  • the wafer and platinum wire are immersed in a 2M NaOH solution.
  • a direct current is applied through the wire and wafer, for example at a density between 10 and 20 mA/cm .
  • Optional UV- illumination is supplied by a 250 W mercury lamp.
  • An appropriate porosity may require 10 to 60 minutes of processing, after which the lamp and the current source are switched off.
  • platinum may be applied directly over the surface of the wafer, or different solutions such as KOH, fluoride acids, or CH 3 OH :HF:H 2 ⁇ 2 are used in a photo-electro- chemically driven process.
  • the density and size of the porosity may be controlled by varying the concentration of the solution.
  • the etching almost exclusively occurs at the tips of the electrolyte-semiconductor interface (ends of the pores); therefore, by altering the solution during etching, a multilayer porosity may be created.
  • a small pore layer at the surface of the template may be produced with a low molarity solution (0.5% KOH).
  • a large pore layer beneath the surface may be produced with a high molarity solution (2% KOH).
  • the small pore layer may be 30-150 nm in thickness and the large pore layer maybe 100-4000 nm in thickness, limited by the stability of the porous material and the thickness of the nonporous material 14 beneath the porous region.
  • electrically conductive GaN is grown on an electrically conductive SiC substrate, porous GaN on porous SiC maybe created by continuing the etching process into the growth substrate, which may permits thinner template growth.
  • porous region 16 air voids are formed in the Ill-nitride material.
  • the voids may be on the order of tens to hundreds of nm in size, for example between 10 and 500 nm in size. Nearest neighbor voids may be spaced on the order of tens to hundreds of nm apart, for example between 10 and 500 nm apart.
  • Porous region 16 may be, for example, between 0.02 and 3 ⁇ m thick.
  • the percent porosity, defined as the volume of voids as a percent of the total volume of porous region 16, can vary from 20-80%, and is often greater than 50%.
  • a relaxed region 26 is grown over porous region 16, as illustrated in Fig. 3.
  • the composition of relaxed region 26 is selected to have a bulk lattice constant different from the bulk lattice constant of Ill-nitride layer 14.
  • Region 26 has a bulk lattice constant that is closer to the bulk lattice constant of light emitting layer 34, as compared to III -nitride layer 14, which may reduce the strain in light emitting layer 34.
  • the composition of relaxed region 26 is selected to have a bulk lattice constant larger than the bulk lattice constant of Ill-nitride layer 14, and often smaller than the bulk lattice constant of a later-grown light emitting layer.
  • the bulk lattice constant of relaxed region 26 is the same as the bulk lattice constant of a light emitting layer.
  • Relaxed region 26 is often InGaN with an InN composition equal to or less than the InN composition in a light emitting layer, or AlInGaN.
  • region 26 Since relaxed region 26 is grown over the discontinuous top surface of porous region 16, region 26 is at least partially relaxed, and as such has an in-plane lattice constant different than the in-plane lattice constant of Ill-nitride layer region 14. Relaxed region 26 initially nucleates on the portions of Ill-nitride material between the voids in porous region 16, then quickly coalesces to form a planar layer, as illustrated in Fig. 3. If relaxed region 26 is InGaN, region 26 is grown thick enough to cover porous region 16. Higher pressure NH3 flow may be used to prevent pits in relaxed region 26.
  • N-type region 32 may include multiple layers of different compositions and dopant concentration including, for example, preparation layers such as buffer layers or nucleation layers which may be n-type or not intentionally doped, release layers designed to facilitate later release of the growth substrate or thinning of the semiconductor structure after substrate removal, and n- or even p-type device layers designed for particular optical or electrical properties desirable for the light emitting region to efficiently emit light.
  • preparation layers such as buffer layers or nucleation layers which may be n-type or not intentionally doped
  • release layers designed to facilitate later release of the growth substrate or thinning of the semiconductor structure after substrate removal
  • n- or even p-type device layers designed for particular optical or electrical properties desirable for the light emitting region to efficiently emit light.
  • at least a portion of relaxed region 26 closest to light emitting region 34 is doped n-type, and separate n-type region 32 is omitted.
  • Light emitting region 34 is grown over n-type region 32.
  • suitable light emitting regions include a single thick or thin light emitting layer, or a multiple quantum well light emitting region including multiple thin or thick quantum well light emitting layers separated by barrier layers.
  • a multiple quantum well light emitting region may include multiple InGaN light emitting layers, each with a thickness of 25 A or less, separated by GaN or InGaN barriers, each with a thickness of 100 A or less.
  • the thickness of each of the light emitting layers in the device is thicker than 50 A.
  • the light emitting region of the device is a single, thick light emitting layer with a thickness between 50 and 600 A, more preferably between 100 and 250 A.
  • the optimal thickness may depend on the number of defects within the light emitting layer.
  • the concentration of defects in the light emitting region is preferably limited to less than 10 9 cm “2 , more preferably limited to less than 10 8 cm “2 , more preferably limited to less than 10 7 cm “2 , and more preferably limited to less than 10 6 cm “2 .
  • At least one light emitting layer in the device is doped with a dopant such as Si to a dopant concentration between IxIO 18 cm “3 and IxIO 20 cm “3 .
  • Si doping may further reduce the strain in the light emitting layer.
  • the light emitting layer or layers are not intentionally doped.
  • P-type region 36 is grown over light emitting region 34.
  • the p-type region may include multiple layers of different composition, thickness, and dopant concentration, including layers that are not intentionally doped, or n-type layers.
  • n-type region 32 and p-type region 36 may depend on the composition of relaxed region 26 over which n-type region 32 is grown.
  • the composition of relaxed region 26 is selected to relax the in-plane lattice constant as much as possible, in order to reduce the strain in the device layers, particularly in the light emitting region. If relaxed region 26 and light emitting region 34 have the same bulk lattice constant and all layers between relaxed region 26 and light emitting region 34 have the same in-plane lattice constant as relaxed region 26, there may be no strain in light emitting region 34.
  • the light emitting region is sandwiched between layers of higher band gap.
  • the higher band gap layers sandwiching the light emitting region have less InN than the light emitting region, which means the higher band gap layers have smaller bulk lattice constants than the light emitting region.
  • the bulk lattice constant and therefore the composition of relaxed region 26 is selected to include as much InN as possible in order to reduce the strain in the light emitting layer as much as possible, while keeping the InN composition in relaxed region 26 low enough that n-type region 32 and p-type region 36 can be grown without cracking at compositions suitable for confining carriers and thicknesses suitable for spreading current from the n- and p-contacts.
  • n-type region 32 is at least 300 nm thick, such that current spreads efficiently through the n-type region for a distance of at least 50 ⁇ m.
  • n-type region 32 may include one or more InGaN layers, or may include one or more Si-doped layers, in order to reduce the amount of tensile strain and thereby increase the thickness at which n-type region 32 may be grown without cracking.
  • n-type layer 32 has the same composition as relaxed region 26, thus n- type layer 32 may be grown to arbitrary thickness, since there is little or no strain in n-type layer 32.
  • the light emitting layers may also have the same composition as relaxed region 26 and n-type region 32, such that there is little or no strain in the light emitting region. Alternatively, the light emitting layers may have a different composition than n-type region 32. The presence of some strain in the light emitting region may improve the internal quantum efficiency and therefore the performance of some device structures.
  • first Ill-nitride region 12 is GaN
  • relaxed region 26 is an Ino osGao 95N region 26 up to 100 nm thick
  • n-type region 32 is a single Ino osGao 95N layer
  • light emitting region 34 includes at least one Ino isGao 85N quantum well layer, a light emitting layer that typically emits blue light.
  • the strain in the Ino isGao 85 N quantum well layer may be less than the strain in a quantum well layer of the same composition and thickness grown in a conventional device.
  • first Ill-nitride region 12 is GaN
  • relaxed region 26 is an Ino iGao 9N region 26 up to 50 nm thick
  • n-type region 32 is a single Ino iGao 9N layer
  • light emitting region 34 includes at least one Ino 2 Gao sN quantum well layer, a light emitting layer that typically emits green light.
  • the strain in the Ino 2 Gao sN quantum well layer may be less than the strain in a quantum well layer of the same composition and thickness grown in a conventional device.
  • first Ill-nitride region 12 is GaN
  • relaxed region 26 is an Ino iGao 9N region 26 up to 50 nm thick
  • n-type region 32 is a single Ino iGao 9N layer
  • light emitting region 34 includes at least one Ino isGao 85 N quantum well layer, a light emitting layer that typically emits blue light.
  • the quantum well layer is sandwiched by thin barrier layers with a larger band gap than the quantum well layer.
  • the barrier layers may be InGaN with a lower InN composition than the quantum well layer, or GaN, grown to a thickness below the critical thickness.
  • the Ino isGao 85N quantum well layer has a bulk lattice constant that is close to that of relaxed region 26 and n-type layer 32, which may reduce the strain in the quantum well layer.
  • first Ill-nitride region 12 is GaN
  • relaxed region 26 is an In 0 05Ga 0 95N region 26 up to 100 nm thick
  • n-type region 32 is a single In 0 05Ga 0 95N layer
  • light emitting region 34 includes at least one Ino isGao 85 N quantum well layer, a light emitting layer that typically emits blue light.
  • the quantum well layer is sandwiched by thin barrier layers with a larger band gap than the quantum well layer.
  • the barrier layers may be InGaN with a lower InN composition than the quantum well layer, or GaN, grown to a thickness below the critical thickness.
  • P-type layer 36 is Ino 05G095N.
  • AlInN Another material that can be used as wider bandgap layers to sandwich lower bandgap InGaN light emitting layers is AlInN.
  • AlInN can be lattice matched to InGaN, with a wider bandgap than InGaN.
  • Fig. 10 is a plot of bandgap as a function of lattice constant for GaN, AlGaN, InGaN and AlInN.
  • AIo 8 2 lno isN is lattice matched to GaN but has a wider bandgap ( ⁇ 4.8eV) than GaN ( ⁇ 3.4eV).
  • AlInN layers formed on at least one side of the light emitting layer may provide lattice matching and carrier confinement in the light emitting layer without excessive optical absorption in the layers sandwiching the light emitting layer.
  • first Ill-nitride region 12 is GaN
  • relaxed region 26 is an Ino isGao 85N region 26 up to 50 nm thick
  • n-type region 32 is a single AlInN layer with an InN composition chosen to lattice-match an Ino isGao 85N light emitting layer, a composition that typically emits blue light. Because the layers beneath the light emitting layer are relaxed, there is no strain in the Ino isGao 85N light emitting layer.
  • P-type region 36 includes at least one AlInN lattice-matched layer and at least one strained GaN layer. To reduce optical absorption in the device, relaxed Ino isGao 85N region 26 may be removed in later processing.
  • relaxed region 26 and n-type region 32 may have a slightly lower InN concentration than the light emitting layer, to provide some strain in the Ino isGao 85 N light emitting layer, but considerably less than a Ino isGao 85 N light emitting layer conventionally grown over GaN.
  • Figs. 5-7 illustrate a second embodiment of a device including a porous region.
  • a mask 50 is formed over the surface of a III -nitride layer 12 grown over a growth substrate, described above in reference to Fig. 1.
  • Openings 52 are formed in mask 50 by conventional patterning techniques.
  • Mask 50 may be, for example, SiN, SiCh, Ti, or TiW, and may be at least 4 nm thick. Openings 52 may vary in size.
  • openings 52 may be a 1 -dimensional pattern, such as stripes, or a 2-dimensional pattern, such as holes.
  • the stripe width or hole diameter may be 2 ⁇ m or less, more preferably less than 500 nm, to reduce the amount of lateral growth necessary for the next-grown layer to coalesce over mask 50.
  • Openings 52 may be spaced 4 ⁇ m apart or less, more preferably 1 ⁇ m apart or less. Large openings may be formed by standard optical lithography. Sub-micron features may be formed by lithography techniques such as imprint or holography, or by stepper- scanners.
  • Portions 54 of III -nitride layer 12 are made porous through openings 52 in mask 50, as illustrated in Fig. 6. Portions 54 may be made porous by one of the techniques described above in reference to Fig. 2. Porous portions 54 are confined to the area directly beneath openings 52 in mask 50. In an alternative embodiment, a porous region is formed before mask 50, then a relaxed region is formed over mask 50.
  • a planar region 56 is grown over mask 50 and the porous regions 54 exposed through the holes 52 in mask 50, for example by a technique such as epitaxial lateral overgrowth. Since region 56 initially nucleates on porous regions 54, region 56 may be at least partially relaxed, as described above in reference to Fig. 3. Initial conditions for growth of region 56 favor the formation of pyramids of material, forcing any defects to bend away from the surface of porous region 54. The growth conditions are then switched to conditions favoring lateral growth. Defects in the crystal may be bent during the pyramid growth, then annihilate during the lateral growth, which may reduce the number of defects that occur from growing on a porous layer.
  • region 56 After region 56 has coalesced, the growth conditions may be switched to conditions that favor normal vertical growth.
  • a device structure including an optional n-type region 32, a light emitting region 34, and a p-type region 36, as described above in reference to Fig. 4, is then grown over relaxed region 56.
  • the light emitting layers in the embodiments described above may have larger in- plane a-lattice constants than light emitting layers grown in conventional devices, which typically have in-plane a-lattice constants no larger than 3.1885 A. Growth of the light emitting layer over a strain-relieved layer at least partially relaxed by a porous layer may increase the in-plane lattice constant to greater than 3.189 A. In some embodiments, the in- plane a-lattice constant in the light emitting layer may be increased to at least 3.195 A, more preferably to at least 3.2 A.
  • An InGaN layer that emits blue light may have the composition Ino i 2 Gao 8 ⁇ N, a composition with a bulk lattice constant of 3.23 A.
  • the strain is (3.189 A - 3.23 A)/3.23 A, about 1.23%. If a light emitting layer of the same composition is grown according to the embodiments described above, the strain may be reduced or eliminated. In some embodiments of the invention, the strain in the light emitting layer of a device emitting light between 430 and 480 nm may be reduced to less than 1%, and more preferably to less than 0.5%.
  • An InGaN layer that emits cyan light may have the composition Ino l ⁇ Gao 8 4 N, a composition with strain of about 1.7 % when grown in a conventional device.
  • the strain in the light emitting layer of a device emitting light between 480 and 520 nm may be reduced to less than 1.5%, and more preferably to less than 1%.
  • An InGaN layer that emits green light may have the composition Ino 2 Gao sN, a composition with a free standing lattice constant of 3.26 A, resulting in strain of about 2.1 % when grown in a conventional device.
  • the strain in the light emitting layer of a device emitting light between 520 and 560 nm may be reduced to less than 2%, and more preferably to less than 1.5%.
  • the semiconductor structures illustrated and described above may be included in any suitable configuration of a light emitting device, such as a device with contacts formed on opposite sides of the device or a device with both contacts formed on the same side of the device.
  • a light emitting device such as a device with contacts formed on opposite sides of the device or a device with both contacts formed on the same side of the device.
  • the device may be formed either with transparent contacts and mounted such that light is extracted either through the same side on which the contacts are formed, or with reflective contacts and mounted as a flip chip, where light is extracted from the side opposite the side on which the contacts are formed.
  • the contact may include a small, thick, absorbing metal bond pad formed over a thin, transparent current spreading layer.
  • the current spreading layer may be, for example, a thin layer of Ni and/or Au, indium tin oxide, Cu-doped InO, ZnO, Ga-doped ZnO, or any other suitable doped, transparent oxide.
  • Fig. 8 illustrates a portion of one example of a suitable configuration, a flip chip device from which the growth substrate has been removed.
  • a portion of p-type region 36 and light emitting region 34 is removed to form a mesa that exposes a portion of n-type region 32.
  • N- and p-contacts 44 and 42 are formed on the exposed parts of n-type region 32 and p-type region 36, for example by evaporating or plating. Contacts 42 and 44 may be electrically isolated from each other by air or a dielectric layer.
  • a wafer of devices may be diced into individual devices, then each device may be flipped relative to the growth direction and mounted on a mount 40, in which case mount 40 may have a lateral extent larger than that of the device.
  • a wafer of devices may be connected to a wafer of mounts, then diced into individual devices.
  • Mount 40 may be, for example, semiconductor such as Si, metal, or ceramic such as AlN, and may have at least one metal pad (not shown) which electrically connects to p-contacts 42 and at least one metal pad (not shown) which electrically connects to the n-contacts 44.
  • Interconnects such as solder or gold stud bumps, connect the semiconductor device to mount 40.
  • Inter-metal dielectrics may be formed on or within mount 40 to electrically isolate the p-type and n-type current paths.
  • the growth substrate is removed by a process suitable to the substrate material, such as etching or laser melting.
  • porous region 16 can be selectively etched to lift off the substrate.
  • a rigid underfill may be provided between the device and mount 40 before or after mounting to support the semiconductor layers and prevent cracking during substrate removal.
  • a portion of the semiconductor structure may be removed by thinning after removing the substrate.
  • porous region 16 and III- nitride region 26 may remain in the finished device, as shown in Fig. 8, or they may be removed by thinning.
  • the exposed surface of the semiconductor structure may be roughened, for example by an etching process such as photoelectrochemical etching or by a mechanical process such as grinding.
  • Roughening the surface from which light is extracted may improve light extraction from the device.
  • a photonic crystal structure may be formed in the top surface of the semiconductor structure exposed by removing the grown substrate.
  • a structure such as a phosphor layer or secondary optics known in the art such as dichroics or polarizers may be applied to the emitting surface.
  • Fig. 9 is an exploded view of a packaged light emitting device, as described in more detail in U.S. Patent 6,274,924.
  • a heat-sinking slug 100 is placed into an insert-molded leadframe.
  • the insert-molded leadframe is, for example, a filled plastic material 105 molded around a metal frame 106 that provides an electrical path.
  • Slug 100 may include an optional reflector cup 102.
  • the light emitting device die 104 which may be any of the devices described in the embodiments above, is mounted directly or indirectly via a thermally conducting submount 103 to slug 100.
  • a cover 108 which may be an optical lens, may be added.
  • the embodiments above describe reducing the strain in a device with InGaN light emitting layers, the techniques and structures described herein may also be used to reduce strain in a device with AlGaN light emitting layers, which typically emit UV light.

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Abstract

A semiconductor structure comprising a Ill-nitride light emitting layer (34) disposed between an n-type region (32) and a p-type region (36) is grown over a porous Ill-nitride region (16, 54). A III -nitride layer (26, 56) comprising InN is disposed between the light emitting layer and the porous Ill-nitride region. Since the Ill-nitride layer comprising InN is grown on the porous region, the Ill-nitride layer comprising InN may be at least partially relaxed, i.e. the III -nitride layer comprising InN may have an in-plane lattice constant larger than an in-plane lattice constant of a conventional GaN layer grown on sapphire.

Description

III-NITRIDE LIGHT EMITTING DEVICE INCLUDING POROUS SEMICONDUCTOR LAYER
BACKGROUND
FIELD OF INVENTION
[0001] The present invention relates to a Ill-nitride light emitting device including a porous layer.
DESCRIPTION OF RELATED ART
[0002] Semiconductor light- emitting devices including light emitting diodes (LEDs), resonant cavity light emitting diodes (RCLEDs), vertical cavity laser diodes (VCSELs), and edge emitting lasers are among the most efficient light sources currently available. Materials systems currently of interest in the manufacture of high-brightness light emitting devices capable of operation across the visible spectrum include Group III -V semiconductors, particularly binary, ternary, and quaternary alloys of gallium, aluminum, indium, and nitrogen, also referred to as Ill-nitride materials. Typically, Ill-nitride light emitting devices are fabricated by epitaxially growing a stack of semiconductor layers of different compositions and dopant concentrations on a sapphire, silicon carbide, Ill-nitride, or other suitable substrate by metal-organic chemical vapor deposition (MOCVD), molecular beam epitaxy (MBE), or other epitaxial techniques. The stack often includes one or more n-type layers doped with, for example, Si, formed over the substrate, one or more light emitting layers in an active region formed over the n-type layer or layers, and one or more p-type layers doped with, for example, Mg, formed over the active region. Electrical contacts are formed on the n- and p-type regions.
SUMMARY
[0003] In accordance with embodiments of the invention, a semiconductor structure comprising a Ill-nitride light emitting layer disposed between an n-type region and a p-type region is grown over a porous Ill-nitride region. A III -nitride layer comprising InN is disposed between the light emitting layer and the porous Ill-nitride region. Since the III- nitride layer comprising InN is grown on the porous region, the Ill-nitride layer comprising InN may be at least partially relaxed, i.e. the Ill-nitride layer comprising InN may have an in- plane lattice constant larger than an in-plane lattice constant of a conventional GaN layer grown on sapphire.
BRIEF DESCRIPTION OF THE DRAWINGS
[0004] Fig. 1 is a cross sectional view of a III -nitride layer grown over a substrate.
[0005] Fig. 2 is a cross sectional view of a porous region formed in a Ill-nitride layer.
[0006] Fig. 3 is a cross sectional view of a relaxed Ill-nitride layer grown over a porous region.
[0007] Fig. 4 is a cross sectional view of a device structure grown over a relaxed III- nitride layer.
[0008] Fig. 5 is a cross sectional view of a mask formed on a Ill-nitride layer grown over a substrate.
[0009] Fig. 6 is a cross sectional view of porous regions formed through openings in a mask.
[0010] Fig. 7 is a cross sectional view of a relaxed Ill-nitride layer grown over the porous regions and the mask.
[0011] Fig. 8 is a cross sectional view of a portion of a Ill-nitride device mounted in flip chip configuration on a mount.
[0012] Fig. 9 is an exploded view of a packaged light emitting device.
[0013] Fig. 10 is a plot of bandgap as a function of lattice constant for InGaN, AlGaN and AlInN alloys.
DETAILED DESCRIPTION
[0014] The performance of a semiconductor light emitting device may be gauged by measuring the external quantum efficiency, which measures the number of photons extracted from the device per electron supplied to the device. The external quantum efficiency is the product of the internal quantum efficiency, defined as the number of photons produced per electron supplied to the device, and the extraction efficiency. The external quantum efficiency may be dominated by the internal quantum efficiency. For simplicity, radiative processes, non-radiative processes, and injection efficiency are all included in the internal quantum efficiency.
[0015] As the current density applied to a conventional Ill-nitride light emitting device increases, the internal quantum efficiency of the device initially increases, then decreases. As the current density increases past zero, the internal quantum efficiency increases, reaching a peak at a given current density (for example, at about 10 A/cm for some devices). As current density increases beyond the peak, the internal quantum efficiency initially drops quickly, then the decrease slows at higher current density (for example, beyond 200 A/cm for some devices). The internal quantum efficiency of a device also decreases as the InN composition in the light emitting region increases, which is required for longer wavelength devices in the Ill-nitride system.
[0016] Since native Ill-nitride growth substrates are generally expensive, not widely available, and impractical for growth of commercial devices, Ill-nitride devices are often grown on sapphire (AI2O3) or SiC substrates. Ill-nitride devices often include GaN, InGaN, and AlGaN layers. For devices that emit visible light, InGaN light emitting layers are often grown over GaN. There is a large lattice mismatch between GaN and the InGaN light emitting layers, resulting in strain in the light emitting layers. This strain limits the thickness and In percentage in the InGaN quantum well. Increasing the thickness of the light emitting layers in the device may increase the current density where the peak in efficiency occurs. This is advantageous for high-current and high-power operation. However, as the thickness and InN composition in the light emitting layers increases, the strain in the light emitting layers also increases. Reducing the strain in the light emitting layers may permit, for a given efficiency, growth of thicker light emitting layers and/or higher InN composition light emitting layers.
[0017] As used herein, an "in-plane" lattice constant refers to the actual lattice constant of a layer within the device, and a "bulk" lattice constant refers to the lattice constant of relaxed, free-standing material of a given composition. The amount of strain in a layer is defined in Eq. (1). strain = ε = (am_plane - abulk)/ abuft: ( 1 )
[0018] Note that strain, ε, in Eq. (1) can be either positive or negative, i.e., ε > 0 or ε < 0. In an unstrained film, a^i^e = abuik , so ε = 0 in Eq. (1). A film where ε > 0 is said to be under tensile strain, or under tension, while a film where ε < 0 is said to be under compressive strain, or under compression. Examples of tensile strain include a strained AlGaN film grown over unstrained GaN, or a strained GaN film grown over unstrained InGaN. In both cases, the strained film has a bulk lattice constant that is smaller than the bulk lattice constant of the unstrained layer on which it is grown, so the in-plane lattice constant of the strained film is stretched to match that of the unstrained layer, giving ε > 0 in Eq. (1). Examples of compressive strain include a strained InGaN film grown over unstrained GaN, or a strained GaN film grown over unstrained AlGaN. In both cases, the strained film has a bulk lattice constant that is larger than the bulk lattice constant of the unstrained layer on which it is grown, so the in-plane lattice constant of the strained film is compressed to match that of the unstrained layer, giving ε < 0 in Eq. (1).
[0019] In a tensile film, the strain pulls the atoms apart from one another in order to increase the in-plane lattice constant. Tensile strain is often undesirable, because the film can respond to the tensile strain by cracking, which decreases the strain in the film, but compromises the structural and electrical integrity of the film. In a compressive film, the strain pushes the atoms together. This effect can reduce the incorporation of large atoms such as indium in an InGaN film, for example, or can negatively impact the material quality of the InGaN light emitting layer in an InGaN LED. In many cases, tensile and compressive strain are both undesirable, and it is beneficial to decrease the tensile or compressive strain in the various layers of the device. In such cases, it is more convenient to refer to the absolute value, or magnitude of the strain, as defined in Eq. (2). As used herein, the term "strain" shall be understood to mean the absolute value, or magnitude of the strain, as defined in Eq. (2).
strain = | ε I = I (am_plane - abuik) | / abulk (2)
[0020] In accordance with embodiments of the invention, a porous semiconductor region is included in a Ill-nitride light emitting device. The porous region may reduce the strain in layers grown over the porous region, particularly in the light emitting layer.
[0021] Figs. 1-4 illustrate a first embodiment of a device including a porous region. As illustrated in Fig. 1, a Ill-nitride layer 12 is grown over a suitable growth substrate 10. III- nitride layer 12 is generally an n-type GaN layer that is not intentionally doped, though it may be an intentionally doped layer (generally n-type), and it may be a binary Ill-nitride material other than GaN, or a ternary or quarternary material such as InGaN, AlGaN, or AlInGaN. Substrate 10 may be, for example, GaN, sapphire, SiC, or a compound substrate such as SiC on Si or SiC on an insulator.
[0022] As illustrated in Fig. 2, all or a portion of layer 12 is made porous. Porous region 16 may be in contact with substrate 10, or may be separated from substrate 10 by a non- porous remaining portion 14 of Ill-nitride layer 12. In embodiments where a sapphire substrate is later removed by laser lift off, the entire thickness of layer 12 may be made porous such that porous material is in direct contact with substrate 10. Porous material at the interface with substrate 10 may reduce the laser power necessary for lift off and thereby reduce the amount of damage to the Ill-nitride material caused by the laser lift off process. For example, layer 12 may be made porous as follows: a platinum wire connected to layer 12 serves as the anode. The other end of the platinum wire serves as the cathode. The wafer and platinum wire are immersed in a 2M NaOH solution. A direct current is applied through the wire and wafer, for example at a density between 10 and 20 mA/cm . Optional UV- illumination is supplied by a 250 W mercury lamp. An appropriate porosity may require 10 to 60 minutes of processing, after which the lamp and the current source are switched off. Alternatively, platinum may be applied directly over the surface of the wafer, or different solutions such as KOH, fluoride acids, or CH3OH :HF:H2θ2 are used in a photo-electro- chemically driven process.
[0023] As taught by, for example, F.K. Yam et al., Porous GaN prepared by UV assisted electrochemical etching, Thin Solid Films 515 (2007) pp. 3469-3474, the density and size of the porosity may be controlled by varying the concentration of the solution. The etching almost exclusively occurs at the tips of the electrolyte-semiconductor interface (ends of the pores); therefore, by altering the solution during etching, a multilayer porosity may be created. To facilitate growth, a small pore layer at the surface of the template may be produced with a low molarity solution (0.5% KOH). Then, to increase the compliance of the template and thereby promote relaxation, a large pore layer beneath the surface may be produced with a high molarity solution (2% KOH). The small pore layer may be 30-150 nm in thickness and the large pore layer maybe 100-4000 nm in thickness, limited by the stability of the porous material and the thickness of the nonporous material 14 beneath the porous region. If electrically conductive GaN is grown on an electrically conductive SiC substrate, porous GaN on porous SiC maybe created by continuing the etching process into the growth substrate, which may permits thinner template growth.
[0024] In porous region 16, air voids are formed in the Ill-nitride material. The voids may be on the order of tens to hundreds of nm in size, for example between 10 and 500 nm in size. Nearest neighbor voids may be spaced on the order of tens to hundreds of nm apart, for example between 10 and 500 nm apart. Porous region 16 may be, for example, between 0.02 and 3 μm thick. The percent porosity, defined as the volume of voids as a percent of the total volume of porous region 16, can vary from 20-80%, and is often greater than 50%.
[0025] A relaxed region 26 is grown over porous region 16, as illustrated in Fig. 3. In general, the composition of relaxed region 26 is selected to have a bulk lattice constant different from the bulk lattice constant of Ill-nitride layer 14. Region 26 has a bulk lattice constant that is closer to the bulk lattice constant of light emitting layer 34, as compared to III -nitride layer 14, which may reduce the strain in light emitting layer 34. In some embodiments the composition of relaxed region 26 is selected to have a bulk lattice constant larger than the bulk lattice constant of Ill-nitride layer 14, and often smaller than the bulk lattice constant of a later-grown light emitting layer. In other embodiments, the bulk lattice constant of relaxed region 26 is the same as the bulk lattice constant of a light emitting layer. Relaxed region 26 is often InGaN with an InN composition equal to or less than the InN composition in a light emitting layer, or AlInGaN.
[0026] Since relaxed region 26 is grown over the discontinuous top surface of porous region 16, region 26 is at least partially relaxed, and as such has an in-plane lattice constant different than the in-plane lattice constant of Ill-nitride layer region 14. Relaxed region 26 initially nucleates on the portions of Ill-nitride material between the voids in porous region 16, then quickly coalesces to form a planar layer, as illustrated in Fig. 3. If relaxed region 26 is InGaN, region 26 is grown thick enough to cover porous region 16. Higher pressure NH3 flow may be used to prevent pits in relaxed region 26.
[0027] Ill-nitride device layers including an n-type region 32, a light emitting region 34, and a p-type region 36, are grown over relaxed region 26, as illustrated in Fig. 4. [0028] N-type region 32 may include multiple layers of different compositions and dopant concentration including, for example, preparation layers such as buffer layers or nucleation layers which may be n-type or not intentionally doped, release layers designed to facilitate later release of the growth substrate or thinning of the semiconductor structure after substrate removal, and n- or even p-type device layers designed for particular optical or electrical properties desirable for the light emitting region to efficiently emit light. In some embodiments, at least a portion of relaxed region 26 closest to light emitting region 34 is doped n-type, and separate n-type region 32 is omitted.
[0029] Light emitting region 34 is grown over n-type region 32. Examples of suitable light emitting regions include a single thick or thin light emitting layer, or a multiple quantum well light emitting region including multiple thin or thick quantum well light emitting layers separated by barrier layers. For example, a multiple quantum well light emitting region may include multiple InGaN light emitting layers, each with a thickness of 25 A or less, separated by GaN or InGaN barriers, each with a thickness of 100 A or less.
[0030] In some embodiments, the thickness of each of the light emitting layers in the device is thicker than 50 A. In some embodiments, the light emitting region of the device is a single, thick light emitting layer with a thickness between 50 and 600 A, more preferably between 100 and 250 A. The optimal thickness may depend on the number of defects within the light emitting layer. The concentration of defects in the light emitting region is preferably limited to less than 109 cm"2, more preferably limited to less than 108 cm"2, more preferably limited to less than 107 cm"2, and more preferably limited to less than 106 cm"2.
[0031] In some embodiments, at least one light emitting layer in the device is doped with a dopant such as Si to a dopant concentration between IxIO18 cm"3 and IxIO20 cm"3. Si doping may further reduce the strain in the light emitting layer. In some embodiments, the light emitting layer or layers are not intentionally doped.
[0032] P-type region 36 is grown over light emitting region 34. Like the n-type region, the p-type region may include multiple layers of different composition, thickness, and dopant concentration, including layers that are not intentionally doped, or n-type layers.
[0033] The composition and thickness of n-type region 32 and p-type region 36 may depend on the composition of relaxed region 26 over which n-type region 32 is grown. The composition of relaxed region 26 is selected to relax the in-plane lattice constant as much as possible, in order to reduce the strain in the device layers, particularly in the light emitting region. If relaxed region 26 and light emitting region 34 have the same bulk lattice constant and all layers between relaxed region 26 and light emitting region 34 have the same in-plane lattice constant as relaxed region 26, there may be no strain in light emitting region 34.
[0034] In some embodiments, it may not be practical to completely eliminate strain in the light emitting region. In order to confine the electrons and holes that combine to create light within the light emitting region, the light emitting region is sandwiched between layers of higher band gap. In devices formed from binary and ternary Ill-nitride layers such as GaN and InGaN, the higher band gap layers sandwiching the light emitting region have less InN than the light emitting region, which means the higher band gap layers have smaller bulk lattice constants than the light emitting region. As a result, if the bulk lattice constants of region 26 and light emitting region 34 are matched to eliminate all strain in the light emitting region, these higher band gap layers sandwiching the light emitting region will be under tensile strain. As the thickness of a layer under tensile strain increases, the layer will eventually crack, or relax, creating defects. Thus, the amount of tensile strain may undesirably limit the thickness to which n- and p-type regions 32 and 36 may be grown.
[0035] In the case of an InGaN region 26 and InGaN light emitting layer, the bulk lattice constant and therefore the composition of relaxed region 26 is selected to include as much InN as possible in order to reduce the strain in the light emitting layer as much as possible, while keeping the InN composition in relaxed region 26 low enough that n-type region 32 and p-type region 36 can be grown without cracking at compositions suitable for confining carriers and thicknesses suitable for spreading current from the n- and p-contacts. In some embodiments, n-type region 32 is at least 300 nm thick, such that current spreads efficiently through the n-type region for a distance of at least 50 μm.
[0036] In some embodiments, n-type region 32 may include one or more InGaN layers, or may include one or more Si-doped layers, in order to reduce the amount of tensile strain and thereby increase the thickness at which n-type region 32 may be grown without cracking. In some embodiments, n-type layer 32 has the same composition as relaxed region 26, thus n- type layer 32 may be grown to arbitrary thickness, since there is little or no strain in n-type layer 32. The light emitting layers may also have the same composition as relaxed region 26 and n-type region 32, such that there is little or no strain in the light emitting region. Alternatively, the light emitting layers may have a different composition than n-type region 32. The presence of some strain in the light emitting region may improve the internal quantum efficiency and therefore the performance of some device structures.
[0037] In a first example, first Ill-nitride region 12 is GaN, relaxed region 26 is an Ino osGao 95N region 26 up to 100 nm thick, n-type region 32 is a single Ino osGao 95N layer, and light emitting region 34 includes at least one Ino isGao 85N quantum well layer, a light emitting layer that typically emits blue light. The strain in the Ino isGao 85N quantum well layer may be less than the strain in a quantum well layer of the same composition and thickness grown in a conventional device.
[0038] In a second example, first Ill-nitride region 12 is GaN, relaxed region 26 is an Ino iGao 9N region 26 up to 50 nm thick, n-type region 32 is a single Ino iGao 9N layer, and light emitting region 34 includes at least one Ino 2Gao sN quantum well layer, a light emitting layer that typically emits green light. The strain in the Ino 2Gao sN quantum well layer may be less than the strain in a quantum well layer of the same composition and thickness grown in a conventional device.
[0039] In a third example, first Ill-nitride region 12 is GaN, relaxed region 26 is an Ino iGao 9N region 26 up to 50 nm thick, n-type region 32 is a single Ino iGao 9N layer, and light emitting region 34 includes at least one Ino isGao 85N quantum well layer, a light emitting layer that typically emits blue light. The quantum well layer is sandwiched by thin barrier layers with a larger band gap than the quantum well layer. The barrier layers may be InGaN with a lower InN composition than the quantum well layer, or GaN, grown to a thickness below the critical thickness. In this example, the Ino isGao 85N quantum well layer has a bulk lattice constant that is close to that of relaxed region 26 and n-type layer 32, which may reduce the strain in the quantum well layer.
[0040] In a fourth example, first Ill-nitride region 12 is GaN, relaxed region 26 is an In005Ga095N region 26 up to 100 nm thick, n-type region 32 is a single In005Ga095N layer, and light emitting region 34 includes at least one Ino isGao 85N quantum well layer, a light emitting layer that typically emits blue light. The quantum well layer is sandwiched by thin barrier layers with a larger band gap than the quantum well layer. The barrier layers may be InGaN with a lower InN composition than the quantum well layer, or GaN, grown to a thickness below the critical thickness. P-type layer 36 is Ino 05G095N.
[0041] Another material that can be used as wider bandgap layers to sandwich lower bandgap InGaN light emitting layers is AlInN. By tuning the AlN and InN compositions, AlInN can be lattice matched to InGaN, with a wider bandgap than InGaN. This is illustrated in Fig. 10, which is a plot of bandgap as a function of lattice constant for GaN, AlGaN, InGaN and AlInN. For example, AIo 82lno isN is lattice matched to GaN but has a wider bandgap (~4.8eV) than GaN (~3.4eV). AlInN layers formed on at least one side of the light emitting layer may provide lattice matching and carrier confinement in the light emitting layer without excessive optical absorption in the layers sandwiching the light emitting layer.
[0042] In a fifth example, first Ill-nitride region 12 is GaN, relaxed region 26 is an Ino isGao 85N region 26 up to 50 nm thick, n-type region 32 is a single AlInN layer with an InN composition chosen to lattice-match an Ino isGao 85N light emitting layer, a composition that typically emits blue light. Because the layers beneath the light emitting layer are relaxed, there is no strain in the Ino isGao 85N light emitting layer. P-type region 36 includes at least one AlInN lattice-matched layer and at least one strained GaN layer. To reduce optical absorption in the device, relaxed Ino isGao 85N region 26 may be removed in later processing. Alternatively, relaxed region 26 and n-type region 32 may have a slightly lower InN concentration than the light emitting layer, to provide some strain in the Ino isGao 85N light emitting layer, but considerably less than a Ino isGao 85N light emitting layer conventionally grown over GaN.
[0043] Figs. 5-7 illustrate a second embodiment of a device including a porous region. As illustrated in Fig. 5, a mask 50 is formed over the surface of a III -nitride layer 12 grown over a growth substrate, described above in reference to Fig. 1. Openings 52 are formed in mask 50 by conventional patterning techniques. Mask 50 may be, for example, SiN, SiCh, Ti, or TiW, and may be at least 4 nm thick. Openings 52 may vary in size. For example, openings 52 may be a 1 -dimensional pattern, such as stripes, or a 2-dimensional pattern, such as holes. The stripe width or hole diameter may be 2 μm or less, more preferably less than 500 nm, to reduce the amount of lateral growth necessary for the next-grown layer to coalesce over mask 50. Openings 52 may be spaced 4 μm apart or less, more preferably 1 μm apart or less. Large openings may be formed by standard optical lithography. Sub-micron features may be formed by lithography techniques such as imprint or holography, or by stepper- scanners.
[0044] Portions 54 of III -nitride layer 12 are made porous through openings 52 in mask 50, as illustrated in Fig. 6. Portions 54 may be made porous by one of the techniques described above in reference to Fig. 2. Porous portions 54 are confined to the area directly beneath openings 52 in mask 50. In an alternative embodiment, a porous region is formed before mask 50, then a relaxed region is formed over mask 50.
[0045] In Fig. 7, a planar region 56 is grown over mask 50 and the porous regions 54 exposed through the holes 52 in mask 50, for example by a technique such as epitaxial lateral overgrowth. Since region 56 initially nucleates on porous regions 54, region 56 may be at least partially relaxed, as described above in reference to Fig. 3. Initial conditions for growth of region 56 favor the formation of pyramids of material, forcing any defects to bend away from the surface of porous region 54. The growth conditions are then switched to conditions favoring lateral growth. Defects in the crystal may be bent during the pyramid growth, then annihilate during the lateral growth, which may reduce the number of defects that occur from growing on a porous layer. After region 56 has coalesced, the growth conditions may be switched to conditions that favor normal vertical growth. A device structure, including an optional n-type region 32, a light emitting region 34, and a p-type region 36, as described above in reference to Fig. 4, is then grown over relaxed region 56.
[0046] The light emitting layers in the embodiments described above may have larger in- plane a-lattice constants than light emitting layers grown in conventional devices, which typically have in-plane a-lattice constants no larger than 3.1885 A. Growth of the light emitting layer over a strain-relieved layer at least partially relaxed by a porous layer may increase the in-plane lattice constant to greater than 3.189 A. In some embodiments, the in- plane a-lattice constant in the light emitting layer may be increased to at least 3.195 A, more preferably to at least 3.2 A.
[0047] An InGaN layer that emits blue light may have the composition Ino i2Gao 8δN, a composition with a bulk lattice constant of 3.23 A. In the case of a conventional Ino i2Gao 8δN layer, the strain is (3.189 A - 3.23 A)/3.23 A, about 1.23%. If a light emitting layer of the same composition is grown according to the embodiments described above, the strain may be reduced or eliminated. In some embodiments of the invention, the strain in the light emitting layer of a device emitting light between 430 and 480 nm may be reduced to less than 1%, and more preferably to less than 0.5%. An InGaN layer that emits cyan light may have the composition Ino lβGao 84N, a composition with strain of about 1.7 % when grown in a conventional device. In some embodiments of the invention, the strain in the light emitting layer of a device emitting light between 480 and 520 nm may be reduced to less than 1.5%, and more preferably to less than 1%. An InGaN layer that emits green light may have the composition Ino 2Gao sN, a composition with a free standing lattice constant of 3.26 A, resulting in strain of about 2.1 % when grown in a conventional device. In some embodiments of the invention, the strain in the light emitting layer of a device emitting light between 520 and 560 nm may be reduced to less than 2%, and more preferably to less than 1.5%.
[0048] The semiconductor structures illustrated and described above may be included in any suitable configuration of a light emitting device, such as a device with contacts formed on opposite sides of the device or a device with both contacts formed on the same side of the device. When both contacts are disposed on the same side, the device may be formed either with transparent contacts and mounted such that light is extracted either through the same side on which the contacts are formed, or with reflective contacts and mounted as a flip chip, where light is extracted from the side opposite the side on which the contacts are formed. In devices where light is extracted through the surface on which the contacts are formed, since current does not spread as readily in p-type Ill-nitride material as in n-type Ill-nitride material, the contact may include a small, thick, absorbing metal bond pad formed over a thin, transparent current spreading layer. The current spreading layer may be, for example, a thin layer of Ni and/or Au, indium tin oxide, Cu-doped InO, ZnO, Ga-doped ZnO, or any other suitable doped, transparent oxide.
[0049] Fig. 8 illustrates a portion of one example of a suitable configuration, a flip chip device from which the growth substrate has been removed. A portion of p-type region 36 and light emitting region 34 is removed to form a mesa that exposes a portion of n-type region 32. Though one via exposing n-type region 32 is shown in Fig. 8, it is to be understood that multiple vias may be formed in a single device. N- and p-contacts 44 and 42 are formed on the exposed parts of n-type region 32 and p-type region 36, for example by evaporating or plating. Contacts 42 and 44 may be electrically isolated from each other by air or a dielectric layer. [0050] After contact metals 42 and 44 are formed, a wafer of devices may be diced into individual devices, then each device may be flipped relative to the growth direction and mounted on a mount 40, in which case mount 40 may have a lateral extent larger than that of the device. Alternatively, a wafer of devices may be connected to a wafer of mounts, then diced into individual devices. Mount 40 may be, for example, semiconductor such as Si, metal, or ceramic such as AlN, and may have at least one metal pad (not shown) which electrically connects to p-contacts 42 and at least one metal pad (not shown) which electrically connects to the n-contacts 44. Interconnects (not shown) such as solder or gold stud bumps, connect the semiconductor device to mount 40. Inter-metal dielectrics may be formed on or within mount 40 to electrically isolate the p-type and n-type current paths.
[0051] After mounting, the growth substrate is removed by a process suitable to the substrate material, such as etching or laser melting. For example, porous region 16 can be selectively etched to lift off the substrate. A rigid underfill may be provided between the device and mount 40 before or after mounting to support the semiconductor layers and prevent cracking during substrate removal. A portion of the semiconductor structure may be removed by thinning after removing the substrate. For example, porous region 16 and III- nitride region 26 may remain in the finished device, as shown in Fig. 8, or they may be removed by thinning. The exposed surface of the semiconductor structure may be roughened, for example by an etching process such as photoelectrochemical etching or by a mechanical process such as grinding. Roughening the surface from which light is extracted may improve light extraction from the device. Alternatively, a photonic crystal structure may be formed in the top surface of the semiconductor structure exposed by removing the grown substrate. A structure such as a phosphor layer or secondary optics known in the art such as dichroics or polarizers may be applied to the emitting surface.
[0052] Fig. 9 is an exploded view of a packaged light emitting device, as described in more detail in U.S. Patent 6,274,924. A heat-sinking slug 100 is placed into an insert-molded leadframe. The insert-molded leadframe is, for example, a filled plastic material 105 molded around a metal frame 106 that provides an electrical path. Slug 100 may include an optional reflector cup 102. The light emitting device die 104, which may be any of the devices described in the embodiments above, is mounted directly or indirectly via a thermally conducting submount 103 to slug 100. A cover 108, which may be an optical lens, may be added. [0053] Though the embodiments above describe reducing the strain in a device with InGaN light emitting layers, the techniques and structures described herein may also be used to reduce strain in a device with AlGaN light emitting layers, which typically emit UV light.
[0054] Having described the invention in detail, those skilled in the art will appreciate that, given the present disclosure, modifications may be made to the invention without departing from the spirit of the inventive concept described herein. Therefore, it is not intended that the scope of the invention be limited to the specific embodiments illustrated and described.

Claims

CLAIMSWhat is being claimed is:
1. A device comprising: a semiconductor structure comprising a Ill-nitride light emitting layer 34 disposed between an n-type region 32 and a p-type region 36; a porous Ill-nitride region 16, 54; and a Ill-nitride layer 26, 56 comprising InN disposed between the light emitting layer and the porous Ill-nitride region.
2. The device of claim 1 wherein the porous III -nitride region 16, 54 is GaN.
3. The device of claim 1 wherein the porous Ill-nitride region 16, 54 comprises a plurality of voids formed in a GaN layer.
4. The device of claim 1 wherein at least 50% of a volume of the porous III- nitride region 16, 54 comprises voids.
5. The device of claim 1 wherein the porous III -nitride region 16, 54 is between 0.02 and 3 μm thick.
6. The device of claim 1 further comprising: a mask layer 50 disposed between the porous Ill-nitride region 54 and the Ill-nitride layer comprising InN 56; and a plurality of openings 52 formed in the mask layer.
7. The device of claim 6 wherein the porous Ill-nitride region is divided into a plurality of regions 54, each of the plurality of porous regions being aligned with an opening 52 in the mask layer 50.
8. The device of claim 1 wherein the III -nitride layer comprising InN 26, 56 has an in-plane lattice constant greater than 3.189 A.
9. The device of claim 1 wherein a volume percent of voids in a first portion of the porous Ill-nitride region 16, 54 is different from a volume percent of voids in a second portion of the porous III -nitride region.
10. A method comprising : growing a first Ill-nitride layer 12 over a substrate 10; making at least a portion 16, 54 of the first Ill-nitride layer porous; growing a second Ill-nitride layer 26, 56 over the porous portion, wherein the second layer comprises InN; and growing a device structure over the second III -nitride layer, the device structure comprising a Ill-nitride light emitting layer 34 disposed between an n-type region 32 and a p- type region 36.
11. The method of claim 10 further comprising: forming a mask 50 over the first Ill-nitride layer 12; and forming a plurality of openings 52 in the mask; wherein growing a second Ill-nitride layer 56 comprises growing by epitaxial lateral overgrowth.
12. The method of claim 11 wherein making at least a portion of the first III- nitride layer 12 porous comprises making regions 54 of the first III -nitride layer aligned with the plurality of openings 52 porous.
13. The method of claim 10 wherein making at least a portion 16, 54 of the first III -nitride layer porous comprises making an entire thickness of the first Ill-nitride layer porous.
14. The method of claim 13 further comprising making at least a portion of the substrate 10 porous.
15. The method of claim 10 wherein making at least a portion of the first III- nitride layer 16, 54 porous comprises making an entire thickness of the first Ill-nitride layer porous, such that porous material is in direct contact with the substrate 10.
PCT/IB2009/051400 2009-04-02 2009-04-02 Iii-nitride light emitting device including porous semiconductor layer Ceased WO2010112980A1 (en)

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