US20020008245A1 - Semiconductor devices with selectively doped iii-v nitride layers - Google Patents
Semiconductor devices with selectively doped iii-v nitride layers Download PDFInfo
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- US20020008245A1 US20020008245A1 US09/442,590 US44259099A US2002008245A1 US 20020008245 A1 US20020008245 A1 US 20020008245A1 US 44259099 A US44259099 A US 44259099A US 2002008245 A1 US2002008245 A1 US 2002008245A1
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- 150000004767 nitrides Chemical class 0.000 title claims abstract description 113
- 239000004065 semiconductor Substances 0.000 title abstract description 7
- 239000002019 doping agent Substances 0.000 claims abstract description 61
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 37
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 36
- 229910052718 tin Inorganic materials 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011777 magnesium Substances 0.000 claims abstract description 22
- 239000010703 silicon Substances 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 19
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 18
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 18
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011135 tin Substances 0.000 claims description 38
- 239000000758 substrate Substances 0.000 claims description 22
- 229910052725 zinc Inorganic materials 0.000 claims description 16
- 239000011701 zinc Substances 0.000 claims description 16
- 238000005336 cracking Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052738 indium Inorganic materials 0.000 claims description 7
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 8
- 229910052782 aluminium Inorganic materials 0.000 claims 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 4
- 229910052757 nitrogen Inorganic materials 0.000 claims 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 230000006835 compression Effects 0.000 claims 1
- 238000007906 compression Methods 0.000 claims 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 abstract description 3
- 229910002601 GaN Inorganic materials 0.000 description 48
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 47
- 239000000463 material Substances 0.000 description 27
- NWAIGJYBQQYSPW-UHFFFAOYSA-N azanylidyneindigane Chemical compound [In]#N NWAIGJYBQQYSPW-UHFFFAOYSA-N 0.000 description 9
- 229910052594 sapphire Inorganic materials 0.000 description 8
- 239000010980 sapphire Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 5
- 208000012868 Overgrowth Diseases 0.000 description 4
- RNQKDQAVIXDKAG-UHFFFAOYSA-N aluminum gallium Chemical compound [Al].[Ga] RNQKDQAVIXDKAG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 description 4
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- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- -1 GaN nitride Chemical class 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- AJGDITRVXRPLBY-UHFFFAOYSA-N aluminum indium Chemical compound [Al].[In] AJGDITRVXRPLBY-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
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- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 description 2
- 229910000083 tin tetrahydride Inorganic materials 0.000 description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
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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
- H10H20/822—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
- H10H20/8252—Materials of the light-emitting regions comprising only Group III-V materials, e.g. GaP containing nitrogen, e.g. GaN characterised by the dopants
-
- 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
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S5/00—Semiconductor lasers
- H01S5/30—Structure or shape of the active region; Materials used for the active region
- H01S5/305—Structure or shape of the active region; Materials used for the active region characterised by the doping materials used in the laser structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S5/00—Semiconductor lasers
- H01S5/30—Structure or shape of the active region; Materials used for the active region
- H01S5/32—Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures
- H01S5/323—Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser
- H01S5/32308—Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser emitting light at a wavelength less than 900 nm
- H01S5/32341—Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser emitting light at a wavelength less than 900 nm blue laser based on GaN or GaP
-
- 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
- H10H20/811—Bodies having quantum effect structures or superlattices, e.g. tunnel junctions
Definitions
- the present invention relates generally to semiconductor devices and more particularly to doping III-V nitride light-emitting devices.
- Si is the donor of choice for doping n-type III-V nitrides due to its favorable properties.
- Si atoms can be delivered to the growing crystal by flowing silane (SiH 4 ), which is available as a high purity grade gas.
- Si incorporates efficiently onto the gallium (Ga) sites in the gallium nitride (GaN) lattice where it acts as a donor.
- Si in GaN (SiGa) is a shallow donor with an activation energy for ionization of ⁇ 20 meV.
- Both a high doping concentration and a large material thickness are desirable to reduce the electrical resistivity of a semiconductor material.
- the doping concentration is limited to ⁇ 5e18 cm ⁇ 3 .
- AlInGaN aluminum indium gallium nitride
- germanium (Ge) and tin (Sn) have been studied as potential donor impurities for III-V nitride materials.
- Ge doping experiments where it was concluded that doping with Ge is problematic.
- S. Nakamura, T. Mukai, and M. Senoh, Si - and Ge - Doped GaN Materials Grown with GaN Buffer Layers Jpn. J. Appl. Phys. 31, 2883, 1992, it is reported that the doping efficiency of Ge is about one order of magnitude lower than for Si.
- the maximum carrier concentration for Ge-doped GaN is limited to ⁇ 1 ⁇ 10 19 cm ⁇ 3 because at this doping level the surface of the Ge-doped GaN materials becomes rough and shows pits.
- X. Zhang, P. Kung, A. Saxler, D. Walker, T. C. Wang, and M. Razeghi Growth of Al x Ga 1-x N:Ge on sapphire and Si substrates , Appl. Phys. Lett. 67 , 1745 ( 1995 ), concluded the Ge-doped aluminum gallium nitride (AlGaN) materials have low electron mobilities and that Ge doping is not useful for growing low resistivity materials.
- AlGaN aluminum gallium nitride
- the present invention provides a semiconductor device having n-type device layers of III-V nitride having donor dopants such as germanium (Ge), silicon (Si), tin (Sn), and/or oxygen (O) and/or p-type device layers of III-V nitride having acceptor dopants such as magnesium (Mg), beryllium (Be), zinc (Zn), and/or cadmium (Cd), either simultaneously or in a doping superlattice, to engineer strain, improve conductivity, and provide longer wavelength light emission.
- donor dopants such as germanium (Ge), silicon (Si), tin (Sn), and/or oxygen (O)
- acceptor dopants such as magnesium (Mg), beryllium (Be), zinc (Zn), and/or cadmium (Cd), either simultaneously or in a doping superlattice, to engineer strain, improve conductivity, and provide longer wavelength light emission.
- the present invention further provides a semiconductor device using Ge either singularly or in combination, as a co-dopant, with Si and Sn as donor dopants either simultaneously or in a doping superlattice to engineer strain.
- the Ge doping concentration can range from ⁇ 10 19 cm ⁇ 3 to ⁇ 10 20 cm ⁇ 3 at layer thicknesses of 3 ⁇ m and higher without causing cracking problems.
- the present invention further provides donor impurities which do not cause embrittlement of III-V nitride materials.
- the present invention further provides multi-donor impurity doping for III-V nitride materials to control doping and strain engineering separately.
- the present invention further provides highly conductive, n-type, Ge-doped, gallium nitride (GaN) materials for utilization in contact layers of III-V nitride devices.
- GaN gallium nitride
- the present invention further provides a light-emitting device with donor impurities which promote growth of high indium nitride (InN) containing indium gallium nitride (InGaN) light emission layers for light emission at long wavelengths ( ⁇ 500 nm).
- InN indium nitride
- InGaN indium gallium nitride
- the present invention further provides a light-emitting device co-doped using a combination of Si, Ge, Sn, oxygen (O), magnesium (Mg), beryllium (Be), zinc (Zn), or cadmium (Cd) to improve the conductivity of III-V nitride materials which stabilize the structural integrity of heteroepitaxially-grown III-V nitride materials on lattice mismatched substrates.
- the present invention further provides a light-emitting device using different donor dopants for conductive and contact layers.
- the present invention further provides a light-emitting device where a bottom layer is doped with Ge and a layer on top doped with a different species (e.g. Si, Sn, or a combination of Si, Ge, and Sn).
- a different species e.g. Si, Sn, or a combination of Si, Ge, and Sn.
- AlGaN aluminum gallium nitride
- the present invention further provides a method of controlling strain and, thus, the effects of piezoelectricity in III-V nitride layers. Strain engineering plays a major role in controlling piezoelectric interface charges.
- FIG. 1 is a light-emitting device incorporating the doped III-V nitride layer of the present invention
- FIG. 2 is a light-emitting device having the doped superlattice of the present invention.
- FIG. 3 is a light-emitting device incorporating the strain engineered doping of the present invention.
- an electronic device such as a light-emitting device 10 which could be a light-emitting diode (LED) or laser diode (LD).
- the light-emitting device 10 includes an optional substrate 11 of sapphire, silicon carbide (SiC), silicon (Si), gallium arsenide (GaAs), or gallium nitride (GaN). It should be understood that the substrate 11 could be discarded in the formation of the light-emitting device 10 after deposition of the various layers which will hereinafter be described.
- the buffer layer 12 is of a material such as GaN or aluminum nitride (AlN) deposited on sapphire at low temperatures around 500° C.
- a highly conductive, n-type, light-emitting, III-V nitride layer 13 is deposited on the buffer layer 12 .
- the nitride layer 13 is made of a doped GaN, an indium gallium nitride (InGaN), an aluminum gallium nitride (AlGaN), an aluminum indium nitride (AlInN), or an aluminum gallium indium nitride (AlGaInN).
- the dopant is germanium (Ge) instead of silicon (Si) or combinations of Si, Ge, tin (Sn), and oxygen (O).
- An active layer 14 is deposited on the nitride layer 13 .
- the active layer 14 can have a single-quantum well (SQW), multiple-quantum well (MQW), or double-hetero (DH) structure.
- this layer is GaN, AlGaN, AlInN, InGaN, or AlInGaN.
- a highly conductive p-type, III-V nitride layer 15 is deposited on the active layer 14 .
- the p-type nitride layer 15 is similar to the n-type nitride layer 13 except with a p-type dopant being used.
- Final device layers 16 such as cladding and/or contact layers, may be deposited on top of the p-type nitride layer 15 .
- the various layers may be grown using techniques such as metal organic chemical vapor deposition (MOCVD), molecular beam epitaxy (MBE), gas source MBE (GSPMBE), or hydride vapor phase epitaxy (HVPE). Also, the composition and/or doping of the various layers may change abruptly from one layer to another, may be smoothly graded over a finite thickness, may be graded over the entire thickness of a layer, or may be combined with undoped layers.
- MOCVD metal organic chemical vapor deposition
- MBE molecular beam epitaxy
- GSPMBE gas source MBE
- HVPE hydride vapor phase epitaxy
- the composition and/or doping of the various layers may change abruptly from one layer to another, may be smoothly graded over a finite thickness, may be graded over the entire thickness of a layer, or may be combined with undoped layers.
- the light-emitting device 20 includes an optional substrate 21 of sapphire, silicon carbide (SiC), silicon (Si), gallium arsenide (GaAs), or gallium nitride (GaN).
- a low temperature buffer layer 22 is often disposed on the substrate 21 .
- the buffer layer 22 is of a material such as GaN or AlN deposited on sapphire at low temperatures.
- a highly conductive, n-type III-V nitride layer is deposited on the buffer layer 22 .
- This nitride layer can be GaN with layers doped with different donors, GaN and InGaN layers doped with different donors, InGaN, AlGaN, and AlGaInN doped with different donors, or these layers with undoped layers in between.
- This layered structure may be termed a “superlattice”, although the layers are thicker than those in a conventional superlattice structures since these layers should range from 10 ⁇ (angstroms) to 10 ⁇ m (microns) in thickness. It has been determined that this greater thickness provides greater strain control.
- the doped layers are designated as nitride layers 23 through 29 , which have combinations of Si, Ge, Sn, and O as dopants.
- the combination of dopants is alternated such that the odd numbered doped nitride layers, designated as nitride layers 23 , 25 , 27 , and 29 , use one or more dopant(s) and the other nitride layers, the even numbered doped nitride layers, designated as nitride layers 24 , 26 , and 28 , use another dopant or combination of dopants to achieve a desired state of strain.
- the nitride layers 23 , 25 , 27 , and 29 are Ge doped and the nitride layers 24 , 26 , and 28 are Si doped.
- An active layer 30 is deposited on the nitride layer 29 .
- the active layer 30 can have a SQW, MQW, or DH structure.
- this layer is an InN containing InGaN or AlInGaN. With a higher InN composition in the InGaN active region, a longer wavelength light emission can be obtained.
- a highly conductive p-type, III-V nitride layer 31 is deposited on the active layer 30 .
- the p-type nitride layer 31 is the same as the n-type nitride layer 23 except with a p-type dopant being used.
- Final device layers 32 such as cladding and/or contact layers, may be deposited on top of the p-type nitride layer 31 .
- the final device layers 32 are the other layers required by the light-emitting device 20 .
- the light-emitting device 50 includes a substrate 51 of sapphire, SiC or GaN. Due to difficulties in nucleation of the single crystalline III-V nitride layers on foreign substrates, a low temperature buffer layer 52 is often deposited on the substrate 51 .
- the buffer layer 52 is of a material such as GaN or AlN.
- a highly conductive, n-type III-V nitride layer is deposited on the buffer layer 52 .
- This nitride layer is made of doped GaN, InGaN, AlGaN, AlInN, or AlGaInN.
- one dopant species is used in a nitride layer designated as nitride layer 53 and a second in a nitride layer designated as nitride layer 54 .
- the dopants are combinations of Si, Ge, Sn, and O.
- the nitride layer 53 is doped with Si and the nitride layer 54 with Ge, the nitride layer 54 can be a contact layer.
- An active layer 55 is deposited on the nitride layers 53 and 54 .
- the active layer 55 can have a SQW or MQW structure.
- this layer is an InN containing InGaN or AlInGaN.
- a highly conductive p-type, III-V nitride layer 56 is deposited on the active layer 55 .
- the p-type nitride layer 56 is similar to the n-type nitride layers 53 and 54 except with a p-type dopant being used.
- Final device layers 57 such as cladding and/or contact layers, may be deposited on top of the p-type nitride layer 56 .
- the final device layers 57 are the other layers required by the light-emitting device 50 .
- Si has been the donor of choice for doping n-type, III-V nitride layers due to its favorable properties.
- Si doping the achievable n-type conductivity of an III-V nitride layer is limited due to the fact that the incorporation of Si leads to the formation of cracks in heteroepitaxially-grown GaN due to differences in lattice constants and in coefficients of thermal expansion with the substrate. It is possible that the cracking problem is a consequence of the small ionic radius of Si donors as compared to Ga host atoms. Si has an ionic radius of 0.41 ⁇ while Ga has an ionic radius of 0.62 ⁇ .
- Si doping leads to more compressive strain in the c-axis direction for high Si doping concentrations.
- the basal plane of GaN is put into more tensile strain.
- Two potential donor impurities, Ge and Sn for III-V nitride materials possess larger ionic radii than Si and are much closer to the ionic radius of Ga.
- Ge has an ionic radius of 0.53 ⁇ and Sn has an ionic radius of 0.71 ⁇ .
- both Ge and Sn doping sources are readily available as gases, germanium hydride (GeH 4 ) and tin hydride (SnH 4 ), for use with conventional MOCVD processes.
- germanium hydride (GeH 4 ) and tin hydride (SnH 4 ) for use with conventional MOCVD processes.
- the donor ionization energies of Ge in GaN (Ge Ga ) and Sn in GaN (Sn Ga ) are expected to be similar to that of silicon in GaN (Si Ga ). This makes these ions ideal dopants.
- the nitride layer 13 can be doped with Si, Ge, Sn, or O alone or together in combination. In contrast to Si-doped GaN, heavily Ge-doped GaN will not crack when grown thicker than ⁇ 1 ⁇ m. Further, the nitride layer 13 with Ge doping levels in the range from ⁇ 10 19 cm ⁇ 3 to ⁇ 10 20 cm ⁇ 3 typically form ohmic contacts with various metals, and thus make good contact layers. Ge doping at such concentration has been deemed to be unobtainable in the literature, as indicated by Nakamura et al, supra.
- the nitride layer 13 may be co-doped using a combination of the following donors: Si, Ge, Sn, and O.
- the different donor species are introduced simultaneously to stabilize the structural integrity of heteroepitaxially-grown III-V nitride on lattice mismatched substrates. For example, tensile strain can be reduced by using combinations of Si and Ge, Si and Sn, and Ge and Sn.
- the use of O is highly desirable as it will occupy the N-lattice site. Hence, there is no site competition with Si, Ge, or Sn which occupies the Ga lattice site, and higher doping levels may be achieved. With higher doping levels, it is possible to achieve much higher conductivity.
- co-dopants of Si/Ge, Si/Sn, and Ge/Sn it is possible to stabilize the lattice and avoid cracking.
- the dopants and their percentages are chosen differently for the growth of GaN, InGaN, and AlGaN to adjust the strain state that is desirable for overgrowth of GaN, AlGaN, AlInN, InGaN, or AlInGaN.
- the light-emitting device 20 is a solution to the problem reported by Nakamura, et al., supra, that the doping efficiency for Ge is an order of magnitude lower than for Si.
- Si layers could be sandwiched between Ge-doped layers so that the total thickness of the Si-doped layers does not exceed the critical thickness for cracking at the given doping level.
- the Si-doped layers 24 , 26 , and 28 would be relatively thin.
- the Ge-doped layers 23 , 25 , 27 , and 29 can be doped to the same concentration, but can be made thick enough to provide the desired high conductivity.
- the different dopants in the nitride layer 13 can be at a single dopant concentration or one which gradually changes from the buffer layer 12 to the nitride layer 13 . It is also practical for the nitride layer 13 to start with one dopant at the buffer layer 12 and gradually decrease the concentration of the one dopant and gradually increase the concentration of the second dopant.
- the strain for subsequent overgrowth of an InGaN or AlGaN active layer 14 will be possible by choosing a specific combination of dopants and grading their relative concentration.
- the in-plane lattice parameters for InGaN and AlGaN are larger and smaller, respectively, than the lattice parameters for GaN.
- the nitride layer 53 of GaN could be doped with Ge. This would allow for high doping and the layer could also be thick.
- a heavily doped nitride layer 54 is grown using a different donor species such as Si which increases the lattice parameter in the c-plane and therefore will allow InGaN with high InN compositions to grow. With a higher InN composition in the InGaN active region, a longer wavelength light emission can be obtained. Also, higher tensile strain in the basal plane will reduce the piezoelectric sheet charge at the InGaN interface.
- the nitride layer 53 would contain GaN:Si and the nitride layer 54 of Ge-doped GaN would be grown on top with a Ge doping concentration of ⁇ 10 20 cm ⁇ 3 .
- This high Ge-doped nitride layer 54 would be a contact layer which is thick enough so that it can be easily reached by etching even if the etch depth varies.
- the active layer 55 is then grown on top of this contact layer.
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Abstract
Description
- The present invention relates generally to semiconductor devices and more particularly to doping III-V nitride light-emitting devices.
- Silicon (Si) is the donor of choice for doping n-type III-V nitrides due to its favorable properties. In particular, during metal-organic chemical vapor deposition (MOCVD), Si atoms can be delivered to the growing crystal by flowing silane (SiH4), which is available as a high purity grade gas. In addition, Si incorporates efficiently onto the gallium (Ga) sites in the gallium nitride (GaN) lattice where it acts as a donor. Further, Si in GaN (SiGa) is a shallow donor with an activation energy for ionization of ˜20 meV.
- However, with Si doping the achievable n-type conductivity of an III-V nitride layer is limited due to the fact that the incorporation of Si leads to the formation of cracks for heteroepitaxially-grown III-V nitride materials (particularly on sapphire substrates). For a given material thickness, the material cracks when the Si doping level exceeds a certain critical concentration. Likewise, for a given doping concentration, the material starts to crack when the material thickness exceeds a certain critical thickness.
- Both a high doping concentration and a large material thickness are desirable to reduce the electrical resistivity of a semiconductor material. For example, for an ˜3.5 μm thick GaN material, as typically employed in a light-emitting diode (LED) structure, the doping concentration is limited to ˜5e18 cm−3. As a consequence of the aforegoing, the series resistance of an aluminum indium gallium nitride (AlInGaN) LED is dominated by the resistance of the Si-doped GaN layer. This is the case for growth on non-conductive substrates such as sapphire where the current passes laterally through the Si-doped GaN layer as well as growth on conductive substrates such as silicon carbide (SiC) and hydride vapor phase epitaxy (HVPE) grown GaN where the current passes vertically through the thick Si-doped GaN layer. Higher doping concentrations and/or thicker n-type GaN materials (for growth on non-conductive substrates) would be advantageous for the fabrication of III-V nitride based LEDs with low series resistance.
- Further, in addition to Si, germanium (Ge) and tin (Sn) have been studied as potential donor impurities for III-V nitride materials. However, there are reports on Ge doping experiments where it was concluded that doping with Ge is problematic. In the S. Nakamura, T. Mukai, and M. Senoh,Si- and Ge-Doped GaN Materials Grown with GaN Buffer Layers, Jpn. J. Appl. Phys. 31, 2883, 1992, it is reported that the doping efficiency of Ge is about one order of magnitude lower than for Si. Furthermore, they concluded that the maximum carrier concentration for Ge-doped GaN is limited to ˜1×1019 cm−3 because at this doping level the surface of the Ge-doped GaN materials becomes rough and shows pits. X. Zhang, P. Kung, A. Saxler, D. Walker, T. C. Wang, and M. Razeghi, Growth of Al x Ga 1-x N:Ge on sapphire and Si substrates, Appl. Phys. Lett. 67, 1745 (1995), concluded the Ge-doped aluminum gallium nitride (AlGaN) materials have low electron mobilities and that Ge doping is not useful for growing low resistivity materials.
- For a long time, a solution has been sought to the problem of material cracking which occurs with Si doping levels exceeding certain concentrations at certain critical thicknesses. Further, Si doping is known to cause the III-V nitride materials to embrittle, which further enhances the tendency of the material to crack, and a solution to this problem has long been sought. It has also been shown that there is a large piezoelectric effect due to the lattice mismatch between GaN and its alloys. For example, an indium gallium nitride (InGaN) layer grown between two GaN layers will have a high piezoelectric sheet charge associated with each interface.
- The present invention provides a semiconductor device having n-type device layers of III-V nitride having donor dopants such as germanium (Ge), silicon (Si), tin (Sn), and/or oxygen (O) and/or p-type device layers of III-V nitride having acceptor dopants such as magnesium (Mg), beryllium (Be), zinc (Zn), and/or cadmium (Cd), either simultaneously or in a doping superlattice, to engineer strain, improve conductivity, and provide longer wavelength light emission.
- The present invention further provides a semiconductor device using Ge either singularly or in combination, as a co-dopant, with Si and Sn as donor dopants either simultaneously or in a doping superlattice to engineer strain. Unlike Si, the Ge doping concentration can range from ˜1019 cm−3 to ˜1020 cm−3 at layer thicknesses of 3 μm and higher without causing cracking problems.
- The present invention further provides donor impurities which do not cause embrittlement of III-V nitride materials.
- The present invention further provides multi-donor impurity doping for III-V nitride materials to control doping and strain engineering separately.
- The present invention further provides highly conductive, n-type, Ge-doped, gallium nitride (GaN) materials for utilization in contact layers of III-V nitride devices.
- The present invention further provides a light-emitting device with donor impurities which promote growth of high indium nitride (InN) containing indium gallium nitride (InGaN) light emission layers for light emission at long wavelengths (λ≧500 nm). This allows the InGaN active region to contain a higher InN composition with higher quality and thus a higher efficiency, longer wavelength light emission or the growth of an AlGaN layer on top of GaN without cracking.
- The present invention further provides a light-emitting device co-doped using a combination of Si, Ge, Sn, oxygen (O), magnesium (Mg), beryllium (Be), zinc (Zn), or cadmium (Cd) to improve the conductivity of III-V nitride materials which stabilize the structural integrity of heteroepitaxially-grown III-V nitride materials on lattice mismatched substrates.
- The present invention further provides a light-emitting device using different donor dopants for conductive and contact layers.
- The present invention further provides a light-emitting device where a bottom layer is doped with Ge and a layer on top doped with a different species (e.g. Si, Sn, or a combination of Si, Ge, and Sn). This permits adjustment of the in-plane lattice constant of GaN closer to the in-plane lattice constant of a ternary compound (e.g., InGaN or aluminum gallium nitride (AlGaN)). This allows the InGaN active region to contain a higher InN composition with higher quality and thus a higher efficiency, longer wavelength light emission or the growth of an AlGaN layer on top of GaN without cracking.
- The present invention further provides a method of controlling strain and, thus, the effects of piezoelectricity in III-V nitride layers. Strain engineering plays a major role in controlling piezoelectric interface charges.
- The above and additional advantages of the present invention will become apparent to those skilled in the art from a reading of the following detailed description when taken in conjunction with the accompanying drawings.
- FIG. 1 is a light-emitting device incorporating the doped III-V nitride layer of the present invention;
- FIG. 2 is a light-emitting device having the doped superlattice of the present invention; and
- FIG. 3 is a light-emitting device incorporating the strain engineered doping of the present invention.
- Referring now to FIG. 1, therein is shown an electronic device such as a light-
emitting device 10 which could be a light-emitting diode (LED) or laser diode (LD). The light-emitting device 10 includes anoptional substrate 11 of sapphire, silicon carbide (SiC), silicon (Si), gallium arsenide (GaAs), or gallium nitride (GaN). It should be understood that thesubstrate 11 could be discarded in the formation of the light-emittingdevice 10 after deposition of the various layers which will hereinafter be described. - Due to difficulties in nucleation of the single crystalline III-V nitride layers on foreign substrates, a low temperature buffer layer12 is often disposed on the
substrate 11. The buffer layer 12 is of a material such as GaN or aluminum nitride (AlN) deposited on sapphire at low temperatures around 500° C. - A highly conductive, n-type, light-emitting, III-
V nitride layer 13 is deposited on the buffer layer 12. Thenitride layer 13 is made of a doped GaN, an indium gallium nitride (InGaN), an aluminum gallium nitride (AlGaN), an aluminum indium nitride (AlInN), or an aluminum gallium indium nitride (AlGaInN). These materials enable low driving voltages for the light-emittingdevice 10 due to reduced resistance in the n-layer, excellent electron injection due to high electron concentration near the p-n junction, and the formation of electrodes to the layers with the ohmic electrical characteristics. In the preferred embodiment, the dopant is germanium (Ge) instead of silicon (Si) or combinations of Si, Ge, tin (Sn), and oxygen (O). - An
active layer 14 is deposited on thenitride layer 13. Theactive layer 14 can have a single-quantum well (SQW), multiple-quantum well (MQW), or double-hetero (DH) structure. Generally, this layer is GaN, AlGaN, AlInN, InGaN, or AlInGaN. - A highly conductive p-type, III-
V nitride layer 15 is deposited on theactive layer 14. The p-type nitride layer 15 is similar to the n-type nitride layer 13 except with a p-type dopant being used. - Final device layers16, such as cladding and/or contact layers, may be deposited on top of the p-
type nitride layer 15. - The various layers may be grown using techniques such as metal organic chemical vapor deposition (MOCVD), molecular beam epitaxy (MBE), gas source MBE (GSPMBE), or hydride vapor phase epitaxy (HVPE). Also, the composition and/or doping of the various layers may change abruptly from one layer to another, may be smoothly graded over a finite thickness, may be graded over the entire thickness of a layer, or may be combined with undoped layers.
- Referring now to FIG. 2, therein is shown an electronic device, such as a light-emitting
device 20. The light-emittingdevice 20 includes anoptional substrate 21 of sapphire, silicon carbide (SiC), silicon (Si), gallium arsenide (GaAs), or gallium nitride (GaN). Again, due to difficulties in nucleation of the single crystalline III-V nitride layers on foreign substrates, a lowtemperature buffer layer 22 is often disposed on thesubstrate 21. Thebuffer layer 22 is of a material such as GaN or AlN deposited on sapphire at low temperatures. - A highly conductive, n-type III-V nitride layer is deposited on the
buffer layer 22. This nitride layer can be GaN with layers doped with different donors, GaN and InGaN layers doped with different donors, InGaN, AlGaN, and AlGaInN doped with different donors, or these layers with undoped layers in between. This layered structure may be termed a “superlattice”, although the layers are thicker than those in a conventional superlattice structures since these layers should range from 10 Å (angstroms) to 10 μm (microns) in thickness. It has been determined that this greater thickness provides greater strain control. - The doped layers are designated as nitride layers23 through 29, which have combinations of Si, Ge, Sn, and O as dopants. The combination of dopants is alternated such that the odd numbered doped nitride layers, designated as nitride layers 23, 25, 27, and 29, use one or more dopant(s) and the other nitride layers, the even numbered doped nitride layers, designated as nitride layers 24, 26, and 28, use another dopant or combination of dopants to achieve a desired state of strain. For example, the nitride layers 23, 25, 27, and 29 are Ge doped and the nitride layers 24, 26, and 28 are Si doped.
- An
active layer 30 is deposited on the nitride layer 29. Theactive layer 30 can have a SQW, MQW, or DH structure. Generally, this layer is an InN containing InGaN or AlInGaN. With a higher InN composition in the InGaN active region, a longer wavelength light emission can be obtained. - A highly conductive p-type, III-
V nitride layer 31 is deposited on theactive layer 30. The p-type nitride layer 31 is the same as the n-type nitride layer 23 except with a p-type dopant being used. - Final device layers32, such as cladding and/or contact layers, may be deposited on top of the p-
type nitride layer 31. The final device layers 32 are the other layers required by the light-emittingdevice 20. - Referring now to FIG. 3, therein is shown another electronic device, such as a light-emitting
device 50. The light-emittingdevice 50 includes asubstrate 51 of sapphire, SiC or GaN. Due to difficulties in nucleation of the single crystalline III-V nitride layers on foreign substrates, a lowtemperature buffer layer 52 is often deposited on thesubstrate 51. Thebuffer layer 52 is of a material such as GaN or AlN. - A highly conductive, n-type III-V nitride layer is deposited on the
buffer layer 52. This nitride layer is made of doped GaN, InGaN, AlGaN, AlInN, or AlGaInN. Here, one dopant species is used in a nitride layer designated as nitride layer 53 and a second in a nitride layer designated as nitride layer 54. In the preferred embodiment, the dopants are combinations of Si, Ge, Sn, and O. Where the nitride layer 53 is doped with Si and the nitride layer 54 with Ge, the nitride layer 54 can be a contact layer. - An
active layer 55 is deposited on the nitride layers 53 and 54. Theactive layer 55 can have a SQW or MQW structure. Generally, this layer is an InN containing InGaN or AlInGaN. - A highly conductive p-type, III-
V nitride layer 56 is deposited on theactive layer 55. The p-type nitride layer 56 is similar to the n-type nitride layers 53 and 54 except with a p-type dopant being used. - Final device layers57, such as cladding and/or contact layers, may be deposited on top of the p-
type nitride layer 56. The final device layers 57 are the other layers required by the light-emittingdevice 50. - In the past, Si has been the donor of choice for doping n-type, III-V nitride layers due to its favorable properties. However, with Si doping the achievable n-type conductivity of an III-V nitride layer is limited due to the fact that the incorporation of Si leads to the formation of cracks in heteroepitaxially-grown GaN due to differences in lattice constants and in coefficients of thermal expansion with the substrate. It is possible that the cracking problem is a consequence of the small ionic radius of Si donors as compared to Ga host atoms. Si has an ionic radius of 0.41 Å while Ga has an ionic radius of 0.62 Å. For example, it has been determined that for growth on c-plane sapphire, Si doping leads to more compressive strain in the c-axis direction for high Si doping concentrations. As a consequence, the basal plane of GaN is put into more tensile strain. Two potential donor impurities, Ge and Sn for III-V nitride materials possess larger ionic radii than Si and are much closer to the ionic radius of Ga. Ge has an ionic radius of 0.53 Å and Sn has an ionic radius of 0.71 Å.
- Further, like Si, both Ge and Sn doping sources are readily available as gases, germanium hydride (GeH4) and tin hydride (SnH4), for use with conventional MOCVD processes. And, the donor ionization energies of Ge in GaN (GeGa) and Sn in GaN (SnGa) are expected to be similar to that of silicon in GaN (SiGa). This makes these ions ideal dopants.
- With reference to the structure shown in FIG. 1, the
nitride layer 13 can be doped with Si, Ge, Sn, or O alone or together in combination. In contrast to Si-doped GaN, heavily Ge-doped GaN will not crack when grown thicker than ˜1 μm. Further, thenitride layer 13 with Ge doping levels in the range from ˜1019 cm−3 to ˜1020 cm−3 typically form ohmic contacts with various metals, and thus make good contact layers. Ge doping at such concentration has been deemed to be unobtainable in the literature, as indicated by Nakamura et al, supra. - Also with reference to FIG. 1, the
nitride layer 13 may be co-doped using a combination of the following donors: Si, Ge, Sn, and O. The different donor species are introduced simultaneously to stabilize the structural integrity of heteroepitaxially-grown III-V nitride on lattice mismatched substrates. For example, tensile strain can be reduced by using combinations of Si and Ge, Si and Sn, and Ge and Sn. In addition, the use of O is highly desirable as it will occupy the N-lattice site. Hence, there is no site competition with Si, Ge, or Sn which occupies the Ga lattice site, and higher doping levels may be achieved. With higher doping levels, it is possible to achieve much higher conductivity. Using co-dopants of Si/Ge, Si/Sn, and Ge/Sn, it is possible to stabilize the lattice and avoid cracking. The dopants and their percentages are chosen differently for the growth of GaN, InGaN, and AlGaN to adjust the strain state that is desirable for overgrowth of GaN, AlGaN, AlInN, InGaN, or AlInGaN. - With reference to FIG. 2, the light-emitting
device 20 is a solution to the problem reported by Nakamura, et al., supra, that the doping efficiency for Ge is an order of magnitude lower than for Si. To circumvent this problem, Si layers could be sandwiched between Ge-doped layers so that the total thickness of the Si-doped layers does not exceed the critical thickness for cracking at the given doping level. Thus, the Si-dopedlayers - Referring back to FIG. 1, the different dopants in the
nitride layer 13 can be at a single dopant concentration or one which gradually changes from the buffer layer 12 to thenitride layer 13. It is also practical for thenitride layer 13 to start with one dopant at the buffer layer 12 and gradually decrease the concentration of the one dopant and gradually increase the concentration of the second dopant. - For example, a gradual adjustment of the strain for subsequent overgrowth of an InGaN or AlGaN
active layer 14 will be possible by choosing a specific combination of dopants and grading their relative concentration. The in-plane lattice parameters for InGaN and AlGaN are larger and smaller, respectively, than the lattice parameters for GaN. - As a consequence, co-doping of a
GaN nitride layer 13 with two different donor species and increasing the concentration of the donor species that increases the in-plane lattice constant towards the interface with an InGaNactive layer 14 will adjust the lattice for overgrowth of InGaN. For example, co-doping with Si and Ge, and increasing Si concentration towards the InGaN interface. - On the other hand, choosing an alternative pair of donor dopants for a
GaN nitride layer 13 and increasing the concentration of the donor that decreases the in-plane lattice constant towards the interface with an AlGaNactive layer 14 will be advantageous for overgrowth of thick AlGaN layers as required for growth of mirror stacks in surface emitting lasers, for example, co-doping with Si and Ge, and increasing Ge concentration towards the AlGaN interface. - With reference now to FIG. 3, similar results to those just described above can be achieved by the introduction of a separately doped layer. For example, the nitride layer53 of GaN could be doped with Ge. This would allow for high doping and the layer could also be thick. On top of the Ge-doped GaN layer, a heavily doped nitride layer 54 is grown using a different donor species such as Si which increases the lattice parameter in the c-plane and therefore will allow InGaN with high InN compositions to grow. With a higher InN composition in the InGaN active region, a longer wavelength light emission can be obtained. Also, higher tensile strain in the basal plane will reduce the piezoelectric sheet charge at the InGaN interface.
- Alternately, the nitride layer53 would contain GaN:Si and the nitride layer 54 of Ge-doped GaN would be grown on top with a Ge doping concentration of ˜10 20 cm−3. This high Ge-doped nitride layer 54 would be a contact layer which is thick enough so that it can be easily reached by etching even if the etch depth varies. The
active layer 55 is then grown on top of this contact layer. - While the invention has been described in conjunction with a specific best mode, it is to be understood that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the aforegoing description. For example, the structure is further applicable to highly doped p-layers in semiconductor devices where the dopants would be Mg, Be, Zn, or Cd. Accordingly, it is intended to embrace all such alternatives, modifications, and variations which fall within the spirit and scope of the included claims. All matters set forth herein or shown in the accompanying drawings are to be interpreted in an illustrative and non-limiting sense.
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PCT/US2000/031646 WO2001037321A2 (en) | 1999-11-17 | 2000-11-17 | Semiconductor devices with selectively doped iii-v nitride layers |
JP2000391607A JP5346146B2 (en) | 1999-11-17 | 2000-11-17 | Semiconductor device having selectively doped III-V nitride layer |
KR1020017008987A KR100735934B1 (en) | 1999-11-17 | 2000-11-17 | Device and light emitting device having a selectively doped III-V nitride layer |
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Also Published As
Publication number | Publication date |
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WO2001037321A3 (en) | 2001-10-11 |
JP5346146B2 (en) | 2013-11-20 |
KR20010108105A (en) | 2001-12-07 |
WO2001037321A2 (en) | 2001-05-25 |
AU1774001A (en) | 2001-05-30 |
EP1175694B1 (en) | 2018-09-26 |
KR100735934B1 (en) | 2007-07-06 |
JP2001210863A (en) | 2001-08-03 |
US6441393B2 (en) | 2002-08-27 |
EP1175694A2 (en) | 2002-01-30 |
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