WO2012110642A1 - Iii-v semiconductor structures with diminished pit defects and methods for forming the same - Google Patents
Iii-v semiconductor structures with diminished pit defects and methods for forming the same Download PDFInfo
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- WO2012110642A1 WO2012110642A1 PCT/EP2012/052784 EP2012052784W WO2012110642A1 WO 2012110642 A1 WO2012110642 A1 WO 2012110642A1 EP 2012052784 W EP2012052784 W EP 2012052784W WO 2012110642 A1 WO2012110642 A1 WO 2012110642A1
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 130
- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000003292 diminished effect Effects 0.000 title abstract description 19
- 230000007547 defect Effects 0.000 title description 11
- 229910052738 indium Inorganic materials 0.000 claims description 139
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 138
- 239000000758 substrate Substances 0.000 claims description 32
- 239000002243 precursor Substances 0.000 claims description 29
- 239000007790 solid phase Substances 0.000 claims description 29
- 238000012545 processing Methods 0.000 claims description 21
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 17
- 229910002601 GaN Inorganic materials 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 6
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 229910021478 group 5 element Inorganic materials 0.000 claims description 5
- 238000010348 incorporation Methods 0.000 claims description 5
- 238000003795 desorption Methods 0.000 claims description 4
- 230000004907 flux Effects 0.000 claims description 4
- 230000003247 decreasing effect Effects 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 52
- 239000007789 gas Substances 0.000 description 23
- 239000012071 phase Substances 0.000 description 22
- 239000013078 crystal Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 235000012431 wafers Nutrition 0.000 description 7
- 229910052733 gallium Inorganic materials 0.000 description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- -1 InO.07GaO.93N) Chemical compound 0.000 description 4
- 238000004630 atomic force microscopy Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000231 atomic layer deposition Methods 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007788 roughening Methods 0.000 description 3
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- KXNLCSXBJCPWGL-UHFFFAOYSA-N [Ga].[As].[In] Chemical compound [Ga].[As].[In] KXNLCSXBJCPWGL-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000000407 epitaxy Methods 0.000 description 2
- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 description 2
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 2
- MNKMDLVKGZBOEW-UHFFFAOYSA-M lithium;3,4,5-trihydroxybenzoate Chemical compound [Li+].OC1=CC(C([O-])=O)=CC(O)=C1O MNKMDLVKGZBOEW-UHFFFAOYSA-M 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OTRPZROOJRIMKW-UHFFFAOYSA-N triethylindigane Chemical compound CC[In](CC)CC OTRPZROOJRIMKW-UHFFFAOYSA-N 0.000 description 2
- 229910002704 AlGaN Inorganic materials 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 208000012868 Overgrowth Diseases 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 101100299498 Xenopus laevis pteg gene Proteins 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- USZGMDQWECZTIQ-UHFFFAOYSA-N [Mg](C1C=CC=C1)C1C=CC=C1 Chemical compound [Mg](C1C=CC=C1)C1C=CC=C1 USZGMDQWECZTIQ-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- NWAIGJYBQQYSPW-UHFFFAOYSA-N azanylidyneindigane Chemical compound [In]#N NWAIGJYBQQYSPW-UHFFFAOYSA-N 0.000 description 1
- 239000003124 biologic agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/38—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C30B29/403—AIII-nitrides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/20—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only AIIIBV compounds
Definitions
- Embodiments of the present invention generally relate to III-V semiconductor structures and methods of forming ⁇ -V semiconductor structures.
- ⁇ -V semiconductor materials such as, for example, ⁇ -arsenides (e.g., Indium Gallium Arsenide (InGaAs)), ⁇ -phosphides (e.g., Indium Gallium Phosphide (InGaP)) and Hi- Nitrides (e.g., Indium Gallium Nitride (InGaN)), may be employed in a number of electronic device structures.
- Some example electronic devices are switching structures (e.g., transistors, etc.), light emitting structures (e.g., laser diodes, light emitting diodes, etc.), light receiving structures (e.g., waveguides, splitters, mixers, photodiodes, solar cells, solar subcells etc.
- Such electronic device structures containing ⁇ -V semiconductor materials may be used in a wide variety of applications. For example, such device structures are often used to produce radiation (e.g., visible light) at one or more of various wavelengths. The light emitted by such structures may be utilized not only for illumination applications, but may also be used in, for example, media storage and retrieval applications, communications applications, printing applications, spectroscopy applications, biological agent detection applications, and image projection applications.
- radiation e.g., visible light
- the light emitted by such structures may be utilized not only for illumination applications, but may also be used in, for example, media storage and retrieval applications, communications applications, printing applications, spectroscopy applications, biological agent detection applications, and image projection applications.
- the InGaN layer may initially grow "pseudomorphically" to the underlying substrate, such that a lattice parameter of the InGaN layer is caused (e.g., forced by atomic forces) to substantially match a lattice parameter of the underlying substrate upon which it is grown.
- the lattice mismatch between the InGaN layer and the underling substrate e.g., GaN
- the lattice mismatch between the InGaN layer and the underling substrate e.g., GaN
- the underling substrate e.g., GaN
- This induced strain may induce a strain energy which may increase with increasing thickness of the InGaN layer.
- the strain energy in the InGaN layer may increase until, at a thickness commonly referred to as the "critical thickness," the InGaN layer may no longer grow in a pseudomorphic manner and may undergo strain relaxation. Strain relaxation in the InGaN layer may result in a deterioration of quality of the InGaN layer.
- such deterioration in crystal quality in the InGaN layer may include the formation of crystalline defects (e.g., dislocations), a roughening of an InGaN layer surface, and/or the formation of regions of inhomogeneous material composition.
- defects may cause the device to be ineffective.
- defects may be significant enough to cause a short across a P-N junction of light emitting diodes (LEDs) or laser diodes, such that the light emitting device cannot generate the desired electromagnetic energy.
- LEDs light emitting diodes
- laser diodes such that the light emitting device cannot generate the desired electromagnetic energy.
- ⁇ -V semiconductor structures and methods for forming such ⁇ -V semiconductor structures that have reduced defect densities to increase the quality of devices formed therewith.
- ⁇ -V semiconductor structures and method for forming them that include Indium alloyed with other materials to form an Indium containing layer with reduced defects densities that is relatively thick, has relatively high Indium concentrations, or combination thereof.
- the various embodiments of the present invention generally relate to ⁇ -V semiconductor structures and methods for forming such ⁇ -V semiconductor structures.
- the present invention includes Indium Gallium Nitride (InGaN) structures and methods of forming InGaN structures.
- InGaN Indium Gallium Nitride
- the present invention includes methods of forming a semiconductor structure comprising forming a ⁇ -V semiconductor layer on a substrate and forming an Indium-III-V semiconductor layer with a diminished V-pit density on a growth surface of the ⁇ - V semiconductor layer.
- the Indium-III-V semiconductor layer is formed with an Indium solid phase concentration above an Indium saturation regime by combining at least an Indium precursor, a group ⁇ element precursor different from the Indium precursor, and a group V element precursor in a processing chamber configured with an Indium super-saturation regime that includes a chamber temperature lower than a corresponding chamber temperature for the Indium saturation regime.
- the present invention includes methods of growing an Indium Gallium Nitride (InGaN) layer.
- a group ⁇ element precursor at a group ⁇ partial pressure is introduced to a processing chamber including a substrate with a ⁇ -V semiconductor layer formed thereon.
- a group V element precursor at a group V partial pressure is introduced to the processing chamber and an Indium precursor at an Indium partial pressure is introduced to the processing chamber.
- An Indium-III-V semiconductor layer is formed with a diminished V-pit density and a thickness greater than a critical thickness by developing an Indium super-saturation regime in the processing chamber that includes a chamber temperature lower than a corresponding chamber temperature for an Indium saturation regime.
- the present invention includes methods of determining processing parameters for an InGaN layer.
- An Indium saturation regime is determined for the InGaN layer over a range of an Indium partial pressure relative to a combined group ⁇ element pressure and substantially constant temperature and pressure for a processing chamber.
- An Indium super-saturation regime is determined that includes a growth-surface temperature lower than that of a growth-surface temperature for the Indium saturation regime wherein the Indium super-saturation regime is sufficient to develop a diminished V-pit density at a higher Indium solid phase concentration.
- the present invention comprises a semiconductor structure including a substrate and a ⁇ -V semiconductor layer formed on the substrate.
- the semiconductor structure also includes an InGaN layer with a diminished V-pit density and an Indium solid phase concentration greater than an Indium solid phase concentration from an Indium saturation regime, wherein the InGaN layer is formed in an Indium super-saturation regime with a chamber temperature lower than that for the Indium saturation regime.
- FIG. 1 is a simplified cross-section drawing of a semiconductor structure with substrate, a III-V semiconductor layer, and a ⁇ - ⁇ -V semiconductor layer formed thereon and illustrating dislocations and V-pits formed therein;
- FIG. 2 is a simplified isometric drawing illustrating a V-pit in an ⁇ - ⁇ -V semiconductor layer
- FIG. 3 is a simplified cross-section drawing of a substrate with a ⁇ -V semiconductor layer and a In-III-V semiconductor layer formed thereon and illustrating a diminished density of V-pits formed therein according to one more embodiments of the invention
- FIG. 4 is a graph of Indium solid phase concentration versus Indium gas phase concentration to illustrate an Indium saturation regime over certain gas phase Indium concentrations
- FIG. 5 is a graph of Indium solid phase concentration versus Indium partial pressure showing the saturation regime of FIG. 4 and super-saturation regimes according to one or more embodiments of the invention.
- FIGS. 6A-6C are graphs illustrating Indium solid phase concentration, V-bit density, and V-pit width, respectively, all relative to Indium partial pressure according to one or more embodiments of the invention.
- any reference to an element herein using a designation such as “first,” “second,” and so forth does not limit the quantity or order of those elements, unless such limitation is explicitly stated. Rather, these designations may be used herein as a convenient method of distinguishing between two or more elements or instances of an element. Thus, a reference to first and second elements does not mean that only two elements may be employed there or that the first element must precede the second element in some manner. Also, unless stated otherwise a set of elements may comprise one or more elements.
- element number indicators begin with the number of the drawing on which the elements are introduced or most fully discussed.
- element identifiers on a FIG. 1 will be mostly in the numerical format lxx and elements on a FIG. 4 will be mostly in the numerical format 4xx.
- the materials described herein may be formed (e.g., deposited or grown) by any suitable technique including, but not limited to, chemical vapor deposition ("CVD”), plasma enhanced chemical vapor deposition (“PECVD”), atomic layer deposition (“ALD”), plasma enhanced ALD, or physical vapor deposition (“PVD”). While the materials described and illustrated herein may be formed as layers, the materials are not limited to layers and may be formed in other three-dimensional configurations.
- CVD chemical vapor deposition
- PECVD plasma enhanced chemical vapor deposition
- ALD atomic layer deposition
- PVD physical vapor deposition
- horizontal and vertical define relative positions of elements or structures with respect to a major plane or surface of a semiconductor structure (e.g., wafer, die, substrate, etc.), regardless of the orientation of the semiconductor structure, and are orthogonal dimensions interpreted with respect to the orientation of the structure being described.
- vertical means and includes a dimension substantially perpendicular to the major surface of a semiconductor structure
- horizontal means a dimension substantially parallel to the major surface of the semiconductor structure.
- semiconductor structure means and includes any structure that is used in the formation of a semiconductor device.
- Semiconductor structures include, for example, dies and wafers (e.g., carrier substrates and device substrates), as well as assemblies or composite structures that include two or more dies and/or wafers three-dimensionally integrated with one another.
- Semiconductor structures also include fully fabricated semiconductor devices, as well as intermediate structures formed during fabrication of semiconductor devices.
- Semiconductor structures may comprise conductive materials, semiconductive materials, non-conductive materials (e.g., electrical insulators), and combinations thereof.
- processed semiconductor structure means and includes any semiconductor structure that includes one or more at least partially formed device structures. Processed semiconductor structures are a subset of semiconductor structures, and all processed semiconductor structures are semiconductor structures.
- ⁇ -V semiconductor means and includes any semiconductor material that is at least predominantly comprised of one or more elements from group ⁇ of the periodic table (e.g., B, Al, Ga, In, and Ti) and one or more elements from group VA of the periodic table (e.g., N, P, As, Sb, and Bi).
- group ⁇ of the periodic table e.g., B, Al, Ga, In, and Ti
- group VA of the periodic table e.g., N, P, As, Sb, and Bi.
- Indium Gallium Nitride and “InGaN” mean alloys of Indium Nitride (InN) and Gallium Nitride (GaN) having a composition of InxGal-xN, where 0 ⁇ x ⁇ l
- critical thickness means the average total thickness of a layer of semiconductor material at which, and beyond which, pseudomorphic growth discontinues and the layer undergoes strain relaxation.
- growth surface means any surface of a semiconductor substrate or layer at which additional growth of the semiconductor substrate or layer can be carried out.
- the term "dislocation” means a region of a semiconductor material where an imperfection of a crystal structure for the semiconductor material exists, which may be characterized by properties such as, for example, missing elements within the crystal structure and broken bonds within the crystal structure.
- Embodiments of the invention may have applications to a wide range of ⁇ -V semiconductor materials.
- the methods and structures of the embodiments of the invention may be applied to ⁇ -Nitrides, Ill-arsenides, ⁇ -phosphides and ⁇ -antimonides, in binary, ternary, quaternary and quinary form.
- Particular applications pertain to growing group Hi- Nitride semiconductors containing Indium, such as Indium Gallium Nitride (InGaN). Accordingly, for conciseness and convenience only, not for limitation, the following description and figures reflect common characteristics of the ⁇ -Nitrides, and may focus particularly on InGaN.
- strain relaxation of the InGaN layer may also result in roughening of the growth surface of the InGaN layer. Such surface roughening may be detrimental to the production of semiconductor devices using the InGaN layer. Further, experimentation has demonstrated that strain relaxation of the InGaN layer may result in an increase in a density of defects in the crystalline material. Such defects may include, for example, dislocations and regions of inhomogeneous composition (i.e., phase separated regions).
- InGaN layers may be deposited heteroepitaxially on an underlying substrate, which may have a crystal lattice that does not match that of the overlying InGaN layer.
- InGaN layers may be deposited on a semiconductor substrate comprising Gallium Nitride (GaN).
- the GaN may have a relaxed (i.e., substantially strain free) in-plane lattice parameter of approximately 3.189 A
- the InGaN layers may have a relaxed in-plane lattice parameter, depending on the corresponding percentage Indium content, of approximately 3.21 A (for 7% Indium, i.e., InO.07GaO.93N), approximately 3.24 A (for 15% Indium, i.e., In0.15Ga0.85N), and approximately 3.26 A (for 25% Indium, i.e., InO.25GaO.75N).
- FIG. 1 is a simplified cross-section drawing of a semiconductor structure 100 with a layer of semiconductor material 130 and an Indium-III-V semiconductor layer 140 formed thereon and illustrating dislocations (132 and 142) and V-pits 150 formed therein.
- the semiconductor structure 100 may be fabricated or otherwise provided to include a substrate 110.
- the substrate 110 may include a semiconductor material that may be used as a seed layer for use in forming one or more additional layers of semiconductor material thereon as part of the fabrication of the layer of semiconductor material 130, and the Indium-III-V semiconductor layer 140, as described in further detail below.
- the layer of semiconductor material 130 may be attached to and carried by the substrate 110. In some embodiments, however, the layer of semiconductor material 130 may comprise a free-standing, bulk layer of semiconductor material that is not disposed on or carried by a substrate or any other material.
- the layer of semiconductor material 130 may comprise an epitaxial layer of semiconductor material.
- the layer of semiconductor material 130 may comprise an epitaxial layer of ⁇ -V semiconductor material.
- the ⁇ -V semiconductor layer 130 may be an epitaxial layer of GaN.
- the substrate 110 may be a material such as, for example, aluminum oxide (A1203) (e.g., sapphire), zinc oxide (ZnO), silicon (Si), silicon carbide (SiC), Gallium arsenide (GaAs), lithium gallate (LiGa02), lithium aluminate (LiA102), yttrium aluminum oxide (Y3A15012), or magnesium oxide (MgO).
- Al oxide e.g., sapphire
- ZnO zinc oxide
- silicon Si
- SiC silicon carbide
- GaAs gallium arsenide
- LiGa02 lithium gallate
- LiA102 lithium aluminate
- Y3A15012 yttrium aluminum oxide
- MgO magnesium oxide
- one or more intermediate layers of material may be disposed between the layer of semiconductor material 130 and the substrate 110.
- Such intermediate layers of material may be used, for example, as a seed layer for forming the layer of semiconductor material 130 thereon, or as a bonding layer for bonding the layer of semiconductor material 130 to the substrate 110, such as might be carried out when it is difficult or impossible to form the layer of semiconductor material 130 directly on the substrate 110.
- bonding of the layer of semiconductor material 130 to the substrate 110 may be desired if the semiconductor material 130 includes polar crystal orientations. In such embodiments, the bonding process may be utilized to alter the polarity of the polar semiconductor material.
- ⁇ -V semiconductor layer 130 may be relatively thin compared to the substrate 110.
- Dislocations may form when the ⁇ -V semiconductor layer 130 is being formed. As illustrated in FIG. 1, these dislocations may be threading dislocations that continue up as the layer is formed with an increasing thickness. In other words, once a dislocation occurs, it may tend to propagate as the layer is formed and would thus appear on a final surface of the ni-V semiconductor layer 130 after its formation is complete.
- Any of various methods known in the art may be used to reduce the density of dislocations in the ⁇ -V semiconductor layer 130. Such methods include, for example, epitaxial lateral overgrowth (ELO), Pendeo epitaxy, in-situ masking techniques, etc.
- the layer of semiconductor material 130 may be deposited, for example, using a process such as metalorganic chemical vapor deposition (MOCVD), molecular beam epitaxy (MBE), or hydride vapor stage epitaxy (HVPE).
- MOCVD metalorganic chemical vapor deposition
- MBE molecular beam epitaxy
- HVPE hydr
- FIG. 1 also illustrates an additional ⁇ -V semiconductor material 140 over the ⁇ - V semiconductor layer 130.
- the additional ⁇ -V semiconductor material 140 may comprise an InGaN layer 140 or Indium in combination with another type of ⁇ - V semiconductor material such as Gallium Phosphide (GaP) and Gallium Arsenide (GaAs).
- GaP Gallium Phosphide
- GaAs Gallium Arsenide
- a semiconductor layer of Indium in combination with a ⁇ -V semiconductor material may be referred to herein as an Indium-III-V semiconductor material or an Indium-III-V semiconductor layer 140.
- InGaN alloy layers grow lattice mismatched on GaN templates (e.g., GaN 130 on sapphire 110). The more Indium in the InGaN layer 140 the larger the lattice mismatch between the InGaN layer 140 and the GaN template.
- the lattice mismatched growth i.e., mismatch between the InGaN layer 140 and the GaN template
- strain relaxation when the strain energy stored in the InGaN layer 140 is greater than the strain energy to nucleate dislocations.
- This lattice mismatched growth occurs for a lattice arranged in cubic systems but is more complex for materials with hexagonal lattice structure like GaN or InGaN or AlGaN.
- thinner InGaN layers 140 can be grown with few or no V-pits 150.
- a thin layer may not reach a thickness (i.e., the critical thickness) at which strain relaxation would occur because the strain energy in the InGaN layer 140 increases with layer thickness.
- thick InGaN layers may be desirable.
- V-pits 150 are present in the thicker InGaN layers 140 and the V-pits 150 become deeper and wider as the InGaN layer 140 becomes thicker.
- V-pits often start from a dislocation, such as threading dislocations shown as 132B and 132D in the ⁇ -V semiconductor layer 130 and as 142A, and 142E in the Indium-ni-V semiconductor layer 140. From these dislocations 132, V-pits (150A, 150B, 150D, and 150E) may form and grow larger as the Indium-III-V semiconductor layer 140 grows. V-pits may also start as an original dislocation as shown with V-pit 150C.
- a dislocation such as threading dislocations shown as 132B and 132D in the ⁇ -V semiconductor layer 130 and as 142A, and 142E in the Indium-ni-V semiconductor layer 140. From these dislocations 132, V-pits (150A, 150B, 150D, and 150E) may form and grow larger as the Indium-III-V semiconductor layer 140 grows. V-pits may also start as an original dislocation as shown with V-pit 150C.
- V-pits 150 can result in holes after further processing for layer transfer, i.e., via smart-cut and bonding processes.
- the V-pits 150 may also locally modify the ion implantation depth and can result in splitting defects.
- further regrowth after layer transfer on the pitted InGaN layers leads to very deep pits that are detrimental for LED device. For example, if a V-pit 150 occurs across the entire InGaN layer 140, it may short out the diode portion of the LED device, rendering the device unable to perform its intended function.
- FIG. 2 is a simplified isometric drawing illustrating a non-limiting example of a V-pit 150 in a non-limiting example ⁇ - ⁇ -V semiconductor layer 140.
- the hexagonal shape of the opening on a growth surface 148 is due to the crystal structure growth of InGaN.
- V- pit sidewallsl 52 lead up from an apex 155 where the V-pit 150 began to form due to the crystal structure growth such that the V-pit 150 generally has a fixed proportion of a width 156 to a depth 154. Therefore, the depth 154 of the V-pit 150 can be accurately estimated based on the width 156 of the V-pit.
- Embodiments of the present invention may reduce the number, size, or a combination thereof of V-pits 150 formed when an Indium-III-V semiconductor layer 130 is formed on a ni-V semiconductor layer 130.
- This reduction in V-pits 150 is also referred to herein as "diminished V-pit density" and "diminished density of V-pits.”
- a diminished V-pit density may refer to fewer V-pits in a given surface area, smaller V-pits in a given surface area, or a combination of fewer V-pits and smaller V-pits in a given surface area.
- Shiojiri M. Shiojiri, C.C.
- embodiments of the present invention may reduce V-pit density by increasing a percentage of Indium in the gas phase during processing, which may saturate the Indium concentration on the ⁇ 0001 ⁇ basal plane of the growth surface 148 of the formed solid material while allowing a higher concentration of Indium on the ⁇ 10-11 ⁇ planes of the V-pit sidewalls 152 to promote growth of InGaN on the V-pit sidewalls.
- FIG. 3 is a simplified cross-section drawing of a semiconductor substrate 110 with a layer of semiconductor material 130 and an Indium-III-V semiconductor layer 140 formed thereon and illustrating a diminished density of V-pits formed therein according to one more embodiments of the invention.
- the semiconductor structure 100 may be fabricated or otherwise provided to include a substrate 110.
- the substrate 110, the layer of semiconductor material 130 and the Indium-III-V semiconductor layer 140 are similar to those described in FIG. 1.
- FIG. 3 illustrates conventional V-pits 152A, 152B, and 152C (i.e., V- pits that may form when conventional processing is used).
- FIG. 3 also illustrates smaller V-pits (158A, 158B, and 158C), which create a diminished density of V-pits according to one or more embodiments of the invention.
- Diminished V-pits 158A and 158C illustrate that the V-pits originating from a threading dislocations 132B and 132C, respectively, have grown at a slower rate (i.e., have not gotten as large) relative to V-pits 152A and 152C that form using conventional processing.
- Diminished V-pit 158B illustrates a smaller V-pit relative to V-pit 152B that may form directly from a dislocation using conventional processing.
- FIG. 4 is a graph of Indium solid phase concentration versus Indium gas phase concentration to illustrate an Indium saturation regime over certain gas phase Indium concentrations.
- FIG. 4 may be developed from experimentation in a processing chamber with a relatively constant temperature, a relatively constant pressure, a relatively constant total gas flow and a relatively constant rotation rate for the wafer. With a specific Gallium flow rate, an Indium flow rate may be varied to vary a percentage of Indium in the gas phase, as shown by the x-axis. The percentage of Indium in the solid phase that develops in the InGaN layer is illustrated on the y- axis as a function of the percentage of Indium in the gas phase.
- an Indium precursor for the formation of the InGaN layer may comprise, for example, trimethylindium (TMI), triethylindium (TEI), or a combination thereof
- a Gallium precursor for the formation of the InGaN layer may comprise, for example, triethylgallium (TEG), or other suitable material.
- a Nitrogen precursor for the formation of the InGaN layer may comprise, for example, ammonia (NH3), or other suitable material.
- FIG. 5 is a graph of Indium solid phase concentration versus Indium partial pressure showing the saturation regime of FIG. 4 and super-saturation regimes according to one or more embodiments of the invention.
- gas flow rate in a processing chamber is related to partial pressure due to each of the different gasses in the processing chamber. Consequently, one can also represent Indium concentration in the gas phase as:
- an N-dopant may comprise a silicon containing vapor such as, for example Silane (S1H4) and a P-dopant may comprise a magnesium containing vapor such as, for example Bis(cyclopentadienyl)magnesium (Cp2Mg).
- the y-axis illustrates percentage of Indium in the solid phase (also referred to herein as Indium concentration in the solid phase) as a function of the x-axis illustrating Indium partial pressure (also referred to herein as Indium concentration in the gas phase).
- Segments 51 OA and 5 I OC illustrate the proportional rise (51 OA) in Indium concentration in the solid phase relative to Indium concentration in the gas phase, followed by the saturation regime wherein the Indium concentration remains relatively constant (510B) with increasing Indium concentration in the gas phase.
- Line 520 illustrates an Indium super-saturation regime wherein a higher concentration of Indium in the solid phase may be obtained relative to the saturation regime.
- Indium super-saturation regime means a condition in a processing chamber configured to develop a higher concentration of Indium in the formed solid phase semiconductor layer relative to what would be formed in the solid phase semiconductor layer using the saturation regime discussed above.
- a saturation regime may be defined as a given chamber pressure, growth surface temperature, ⁇ element precursor partial pressure, V element precursor partial pressure, and Indium precursor partial pressure.
- a higher concentration or partial pressure of the Indium precursor relative to that of the saturation regime may develop a super-saturation regime that forms a higher concentration of Indium in the formed semiconductor layer.
- a reduction in the growth surface temperature may create a super-saturation regime yielding a solid phase growth condition that develops a higher Indium percentage in the formed semiconductor layer relative to what would be obtained for the saturation regime.
- an increase in chamber pressure, or change in wafer rotation rate, while holding temperature at the saturation regime temperature may develop an Indium super-saturation regime.
- chamber parameters such as, for example, chamber pressure and wafer rotation rate, may be held relatively constant and the temperature reduced to develop the Indium super-saturation regime. Temperature may be determined as chamber temperature or growth-surface temperature. As a non-limiting example, the chamber temperature for segments 51 OA and 51 OB is about 839 °C and the chamber temperature for line 520 is about 811 °C.
- relative concentration between group ⁇ precursors e.g., an Indium precursor combined with a Gallium precursor
- the partial pressure for TEG may remain relatively constant and as the partial pressure for TMI increases the partial pressure for ammonia proportionally increases to keep the V/ ⁇ ratio at about 3560.
- Line 530 may be developed with a chamber temperature of about 811 °C and a group V partial pressure (e.g., a partial pressure of ammonia) held substantially constant relative to the group ⁇ partial pressure and the varying Indium partial pressure.
- group V partial pressure e.g., a partial pressure of ammonia
- the partial pressure for TEG and ammonia may remain relatively constant while the partial pressure for TMI increases.
- the flow of Indium precursor to the InGaN layer 140 may affect the incoming flux of Indium species available for interaction on the growth surface 148 and the V-pit sidewalls 152.
- Indium can be highly volatile.
- TMI will break down and release the metal (.e.g., Indium) that can incorporate into the solid layer or dissipate as a vapor. With a higher temperature, the higher the likelihood that the metal will dissipate rather than incorporate.
- FIGS. 6A-6C are graphs illustrating Indium solid phase concentration, V-pit density, and V-pit width, respectively, all relative to Indium partial pressure according to one or more embodiments of the invention.
- line 610 in FIG. 6A As can be seen by line 610 in FIG. 6A, as the Indium concentration in the gas phase increases the Indium concentration in the solid phase also increases up to an Indium concentration of about 94%. At that point, increases in gas phase concentration lead to lower solid phase concentrations.
- the pit width is a preferred way to measure V-pits with Atomic Force Microscopy (AFM) as the AFM tip may not be sharp enough to penetrate the entire depth of the V-pit to measure the depth correctly. From crystallographic (e.g., the angle between (10-11) and (0001) planes) considerations a pit depth can be calculated from the pit width (J.E. Northrup, L.T. Romano, J. Neugebauer, Appl. Phys. Lett. 74(6), 2319 (1999).
- AFM Atomic Force Microscopy
- V-pits may exist but are not detectible because their widths may be below the resolution of AFM.
- Some embodiments of the present invention may generate diminished V-pit densities for solid phase Indium concentrations in the range of about 6% to 9%.
- the diminished V-pit densities may be achieved for relatively thick InGaN layers of about 150 nanometers and possibly up to about 200 nanometers.
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