WO2016125993A1 - Diode électroluminescente émettant dans l'ultraviolet - Google Patents

Diode électroluminescente émettant dans l'ultraviolet Download PDF

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Publication number
WO2016125993A1
WO2016125993A1 PCT/KR2015/011997 KR2015011997W WO2016125993A1 WO 2016125993 A1 WO2016125993 A1 WO 2016125993A1 KR 2015011997 W KR2015011997 W KR 2015011997W WO 2016125993 A1 WO2016125993 A1 WO 2016125993A1
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WO
WIPO (PCT)
Prior art keywords
layer
light emitting
emitting diode
composition ratio
ultraviolet light
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PCT/KR2015/011997
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English (en)
Korean (ko)
Inventor
박승환
서대웅
Original Assignee
서울바이오시스 주식회사
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Priority claimed from KR1020150031807A external-priority patent/KR20160097098A/ko
Application filed by 서울바이오시스 주식회사 filed Critical 서울바이오시스 주식회사
Publication of WO2016125993A1 publication Critical patent/WO2016125993A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/04—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
    • H01L33/06—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/12—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a stress relaxation structure, e.g. buffer layer

Definitions

  • the present invention relates to an ultraviolet light emitting diode, and more particularly, to an ultraviolet light emitting diode having an active layer structure in which internal quantum efficiency can be improved.
  • an active layer is made of a material having a bandgap energy corresponding to the emission wavelength of the ultraviolet band.
  • an active layer of an ultraviolet light emitting diode manufactured using a nitride semiconductor includes a nitride semiconductor including Al, for example, an active layer in which a well layer is formed of AlGaN and a barrier layer of AlGaN or AlN is adopted for the ultraviolet light emitting diode.
  • a nitride semiconductor layer having a higher Al composition ratio is required to be applied to the active layer.
  • the characteristics of the active layer including AlGaN are different from those of general blue light emitting diodes, and thus, an active layer structure capable of increasing the internal quantum efficiency of the ultraviolet light emitting diodes is required.
  • the problem to be solved by the present invention is to provide an ultraviolet light emitting diode having a high luminous efficiency, in particular, the internal quantum efficiency is improved to increase the amount of light.
  • the barrier layer may include Al z Ga (1-z) N (0 ⁇ z ⁇ 1), and the barrier layer may have a greater bandgap energy than the well layer.
  • Y may be greater than or equal to 0 and less than or equal to 0.2 and 0 ⁇ x ⁇ 0.12.
  • the y may be 0.2 or more and 0.4 or less and 0 ⁇ x ⁇ 0.07.
  • the amount of TE-polarized light in the light emitted from the active layer, may be greater than the amount of TM-polarized light.
  • an ultraviolet light emitting diode includes a well layer including BAlGaN, thereby providing an ultraviolet light emitting diode having improved internal quantum efficiency. Also, by forming a BAlGaN well layer having a composition ratio of Al and B in a predetermined range, the light amount of TE-polarized light can be increased, so that the substantial light amount of light emitted from the ultraviolet light emitting diode can be increased.
  • FIG. 1 is a cross-sectional view illustrating a structure of an ultraviolet light emitting diode according to an embodiment of the present invention.
  • FIG. 2 is an enlarged cross-sectional view illustrating the structure of an active layer according to an embodiment of the present invention.
  • 3 to 6 are graphs for explaining characteristics of light emitting diodes according to exemplary embodiments of the present invention and a comparative example.
  • composition ratio, growth method, growth conditions, thickness, etc. for the semiconductor layers described below correspond to an example, and the present invention is not limited as described below.
  • the composition ratio of Al and Ga may be variously applied according to the needs of those skilled in the art.
  • the semiconductor layers described below can be grown using a variety of methods generally known to those skilled in the art (hereinafter referred to as "normal technician"), for example, MOCVD (Metal Organic Chemical) It may be grown using techniques such as Vapor Deposition, Molecular Beam Epitaxy (MBE), or Hydride Vapor Phase Epitaxy (HVPE).
  • sources introduced into the chamber may use a source known to a person skilled in the art.
  • TMGa, TEGa, etc. may be used as a Ga source. and, as an Al source, and you can take advantage of a TMA, TEA, etc., as the In source may be used, and TMI, TEI, NH 3 may be used as the N source.
  • TMGa, TEGa, etc. may be used as a Ga source.
  • Al source and you can take advantage of a TMA, TEA, etc., as the In source may be used, and TMI, TEI, NH 3 may be used as the N source.
  • TMI, TEI, NH 3 may be used as the N source.
  • the present invention is not limited thereto.
  • FIG. 1 is a cross-sectional view illustrating a structure of a light emitting diode according to an embodiment of the present invention
  • FIG. 2 is an enlarged cross-sectional view illustrating a structure of an active layer 400 according to an embodiment of the present invention.
  • the ultraviolet light emitting diode includes a first conductive semiconductor layer 300, an active layer 400, and a second conductive semiconductor layer 500.
  • the light emitting diode may further include a substrate 100 and a buffer layer 200.
  • the substrate 100 is not limited as long as it is a substrate for growing a nitride semiconductor layer, and may be, for example, a sapphire substrate, a silicon carbide substrate, a spinel substrate, or a nitride substrate such as a GaN substrate or an AlN substrate.
  • the substrate 100 may be omitted as necessary.
  • the substrate 100 may be separated and removed from the semiconductor layers.
  • the substrate 100 may be removed through laser lift off, stress lift off, chemical lift off, or physicochemical methods through lapping or polishing.
  • the buffer layer 200 is located on the substrate 100.
  • the buffer layer 200 may include a nuclear layer that helps other semiconductor layers grown on the substrate 100 to grow into a single crystal, and may include a three-dimensional growth layer and a recovery layer positioned on the nuclear layer.
  • the buffer layer 200 may also serve to alleviate stress caused by a difference in lattice constant between the substrate 100 and other semiconductor layers grown on the buffer layer 200.
  • the buffer layer 200 may include a nitride semiconductor such as (Al, Ga, In) N, and may include, for example, at least one of GaN, AlGaN, and AlN. In the present embodiment, the buffer layer 200 may include AlN.
  • the buffer layer 200 may be omitted.
  • the first conductive semiconductor layer 300 is grown on the substrate 100 without additionally forming the buffer layer 200. Can be.
  • the buffer layer 200 may also be removed in the process of separating the substrate 100.
  • the first conductivity type semiconductor layer 300 may include a nitride semiconductor such as (Al, Ga, In) N. Since the ultraviolet light emitting diode according to the present embodiment emits light in the ultraviolet band, the first conductivity type semiconductor layer 300 may include a nitride semiconductor that does not absorb light in the ultraviolet band. Specifically, when the bandgap energy of the nitride semiconductor forming the first conductivity type semiconductor layer 300 is smaller than the energy corresponding to the wavelength of the light of the ultraviolet band, the light of the ultraviolet band may be absorbed by the nitride semiconductor. When the light is absorbed by the nitride semiconductor, the luminous efficiency of the ultraviolet light emitting diode may be very low.
  • a nitride semiconductor such as (Al, Ga, In) N. Since the ultraviolet light emitting diode according to the present embodiment emits light in the ultraviolet band, the first conductivity type semiconductor layer 300 may include a nitride semiconductor that does not absorb light in the ultraviolet band. Specifically, when
  • the first conductivity type semiconductor layer 300 may include Al, and in particular, may include AlGaN.
  • the Al composition ratio of the AlGaN may be adjusted according to the wavelength of light emitted from the active layer 400. For example, when the peak wavelength of the light emitted from the active layer 400 is 400 nm or less, the AlGaN may have an Al composition ratio of about 0.2 or more. When the peak wavelength of the light emitted from the active layer 400 is 300 nm or less, the AlGaN is about 0.4. It may have an Al composition ratio of more than.
  • the present invention is not limited thereto.
  • the first conductive semiconductor layer 300 may have an n-type or p-type conductive type, including an n-type or p-type dopant.
  • the first conductivity type semiconductor layer 300 may be doped to n-type by including impurities such as Si, Ge, and the like as a dopant.
  • the first conductivity type semiconductor layer 300 may be a single layer or may be formed of multiple layers including a plurality of layers.
  • the first conductivity type semiconductor layer 300 may include a clad layer, a contact layer, a superlattice layer, or the like.
  • the first conductivity type semiconductor layer 300 may include a gradient layer in which the composition ratio continuously changes.
  • the active layer 400 may include a nitride semiconductor such as (Al, Ga, In) N, and may control the composition ratio of the nitride semiconductor to emit light having a peak wavelength in a desired ultraviolet region.
  • the active layer 400 may include a multi-quantum well structure (MQW) in which the well layer 410 and the barrier layer 420 are alternately stacked.
  • MQW multi-quantum well structure
  • the barrier layer 420 may include a nitride semiconductor having a greater bandgap energy than the well layer 410, and may include Al z Ga (1-z) N (0 ⁇ z ⁇ 1).
  • the barrier layer 420 may be formed of AlN.
  • the barrier layer 420 is formed of a nitride semiconductor having a relatively higher bandgap energy than the well layer 410, thereby allowing a plurality of carriers (electrons and holes) to concentrate on the well layer 410. This increases the probability that electrons and holes combine.
  • the well layer 410 may include a nitride semiconductor having a bandgap energy smaller than the barrier layer 420.
  • the well layer 410 includes B (boron), for example, B x Al y Ga (1-xy) N (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1 and x ⁇ y). have. Since the well layer 410 further includes B in addition to AlGaN, an absolute value of an internal field inside the well layer 410 may be reduced. This is achieved by the well layer 410 further comprising B, whereby the degree of lattice mismatch is reduced. Accordingly, spatial separation of the conduction and valence bands in the active layer 400 may be reduced, thereby improving recombination efficiency of electrons and holes. In addition, as the spatial separation of the conduction band and the valence band is reduced, the phenomenon of increasing the transition wavelength of the light emitting diode can be prevented.
  • the composition ratio of Al may be greater than 0 and less than 0.5. In this case, the effect of increasing the luminous efficiency when B is added to AlGaN can be further improved.
  • the composition ratio of Al is 0.5 or more, the addition of B causes the uppermost subband in the valence band to change from a heavy-hole band to a crystal-field splittoff hole band, thus transverse-electric ) -Polarized light is reduced and transverse-magnetic (TM) -polarized light is increased. That is, when the composition ratio of Al is 0.5 or more, the luminous efficiency of the light emitting diode is reduced. Therefore, in the ultraviolet light emitting diode emitted light of this embodiment, the light amount of TE-polarized light is larger than the light amount of TM-polarized light.
  • the composition ratio of B has a constant dependency on the composition ratio of Al.
  • the composition ratio x of B in B x Al y Ga (1-xy) N is lower than the composition ratio y of Al.
  • the composition ratio x of B may be greater than 0 and 0.12 or less, and further, the composition ratio x of B may be 0.06 or more and 0.10 or less.
  • the composition ratio (y) of Al when the composition ratio (y) of Al is 0.2 or more and 0.4 or less, the composition ratio (x) of B may be more than 0 and 0.07 or less, and further, the composition ratio (x) of B may be 0.02 or more and 0.06 or less.
  • the higher the Al composition ratio, the lower the optimum composition ratio of B, and the Al composition ratio and the B composition ratio may be in a linear relationship with each other. The relation of -5x + (0.5 ⁇ 0.7) can be satisfied.
  • the AlGaN well layer containing no B is determined by determining the composition ratio x of B and the composition ratio y of Al in the above-mentioned ranges. Luminous efficiency can be improved compared with the case where it is used.
  • FIGS. 3 to 6 are graphs for explaining characteristics of light emitting diodes according to exemplary embodiments of the present invention and a comparative example.
  • 4A shows an optical matrix element value (
  • 4B shows the strain and the internal field of the well layer according to the composition ratio of B.
  • FIG. 5A shows a spontaneous emission coefficient according to the wavelength when x is 0, 0.02, 0.06, 0.10 and 0.12
  • FIG. 5B shows the spontaneous emission coefficient according to the composition ratio of B. (spontaneous emission coefficient).
  • 6 (a) to 6 (c) show potential profiles and wave functions when x is 0, 0.06, and 0.12 according to positions
  • FIG. 6 (d) shows pseudo Fermi levels according to the composition ratio of B (Quasi ⁇ ).
  • the graph of FIG. 3 was derived according to a self-consistent solution, which was calculated assuming a carrier density (N 2D ) of 20 ⁇ 10 12 cm ⁇ 2 .
  • 'HHn', 'LHn' and 'CHn' in FIGS. 3 and 6 are 'n-th heavy-hole subband', 'n-th light-hole subband' and 'n-th crystal splitting hole subband (crystal), respectively.
  • -field splittoff hole subband) ' '.
  • the energy of each subband changes according to the composition ratio x of B.
  • the uppermost subband of the valence band is represented by HH1.
  • the energy of the crystal splitting hole subband CH1 increases and is located between LH1 and HH2.
  • the heavy-hole effective mass increases as B is added to AlGaN.
  • the composition ratio (x) of B in the BAlGaN / AlN quantum well structure is 0 and 0.12
  • the heavy-hole effective mass is respectively. 1.75m 0 and 2.97m 0 .
  • the light amount of TE-polarized light increases as the composition ratio x of B increases.
  • the x value is 0.1 or more
  • the amount of light of the TE-polarized light is drastically reduced when the plane wave vector k ⁇ increases above a certain size. This is interpreted as the uppermost subband in the valence band is changed from the heavy-hole band (HH) to the crystal splitting hole band (CH) when the amount of B added is more than a predetermined value.
  • the emission wavelength is shortened as the composition ratio x of B increases from 0 to 0.12, and the amount of light of TE-polarized light increases.
  • the composition ratio y of Al is less than 0.5, the amount of light of TE-polarized light increases by adding B to the well layer. That is, as described with reference to FIGS. 3 and 4, by adding B to the well layer, the luminous efficiency of the ultraviolet light emitting diode is improved.
  • composition ratio x of B exceeds the threshold of the predetermined ratio, it can be seen that the amount of light emitted from the light emitting diode is reduced.
  • the composition ratio y of Al is 0.2
  • B Increasing the composition ratio (x) from 0 to 0.08 increases the amount of light
  • the composition ratio (x) of B is more than 0.08, the amount of light decreases with the increase in the B composition ratio.
  • composition ratio y of Al when the composition ratio y of Al is 0.4, when the composition ratio x of B is increased from 0 to 0.04, the amount of light increases, but the composition ratio x of B is greater than 0.04.
  • the amount of light decreases with the increase in the B composition ratio.
  • the composition ratio y of Al is 0.6, the amount of light decreases even if B is added.
  • the amount of light decreases.
  • the uppermost subband in the valence band has a heavy-hole band ( It is interpreted as changing from HH) to crystal splitting hole band (CH). It is also interpreted that the light amount of the TM-polarized light increases simultaneously with the decrease in the light amount of the TE-polarized light.
  • B x Al 0 B x Al 0 .
  • Increasing the B composition ratio (x) from 2 Ga (0.8-x) N to 0.12 reduces the spatial separation of the energy bands and the spatial separation of the wavefunction. As described above, this is an effect due to the reduction of the internal field, and thus, by adding B, the internal quantum efficiency of the ultraviolet light emitting diode can be increased.
  • FIG. 6D it can be seen that the pseudo Fermi level separation ( ⁇ E fc + ⁇ E f ⁇ ) decreases as the B composition ratio increases.
  • the pseudo Fermi level separation ( ⁇ E fc + ⁇ E f ⁇ ) is defined as the difference between the energy of the pseudo Fermi level and the energy of the ground state. Accordingly, it can be seen that the luminous efficiency improves with the addition of B. However, when the composition ratio of B exceeds 0.8, the value of ⁇ E fc + ⁇ E f ⁇ is lower than ⁇ E fc , and it is interpreted that the amount of light of TE-polarized light decreases with increasing B again.
  • the matrix element is related to the transition probability of electrons and holes, and as the TE optical matrix element increases, the emission intensity increases, but the maximum value is determined because the separation energy of the quasi fermi level gradually decreases. .
  • the Al component exceeds 0.5, the optimum point disappears because the TE optical matrix element suddenly decreases regardless of the separation energy of the pseudo Fermi level. Therefore, while satisfying the above relation, satisfying 0 ⁇ y ⁇ 0.5 and 0 ⁇ x ⁇ y, the TE optical matrix element can be maximized to obtain higher luminous efficiency.
  • the second conductivity type semiconductor layer 500 is located on the active layer 400.
  • the second conductivity-type semiconductor layer 500 may include a nitride semiconductor such as (Al, Ga, In) N, and may include, for example, AlGaN or GaN.
  • the second conductivity-type semiconductor layer 500 may be doped with a conductivity type opposite to that of the first conductivity-type semiconductor layer 300, and may have, for example, a p-type conductivity type including an Mg dopant.
  • the second conductivity-type semiconductor layer 500 may further include a delta doping layer (not shown) for lowering ohmic contact resistance, and may further include an electron blocking layer (not shown).
  • an ultraviolet light emitting diode having improved internal quantum efficiency, increased TE polarized light, improved light extraction efficiency, and increased emission intensity can be provided.
  • the ultraviolet light emitting diode may implement ultraviolet light of various wavelengths, and in particular, an ultraviolet light emitting diode that emits deep ultraviolet light (including light in the UVC band) may be provided.
  • the structure of the ultraviolet light emitting diode of FIG. 1 may be modified in various forms. For example, by performing an additional process to the ultraviolet light emitting diode structure of FIG. 1, light emitting diodes having various known structures, such as a horizontal type, a vertical type, or a flip chip type, may be implemented.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Led Devices (AREA)

Abstract

Cette invention concerne une diode électroluminescente émettant dans l'ultraviolet Ladite diode électroluminescente émettant dans l'ultraviolet comprend : une première couche conductrice de semi-conducteur; une couche active qui est disposée sur la première couche conductrice de semi-conducteur et comprend une couche de puits comprenant BxAlyGa(1-x-y)N et une couche barrière; et une seconde couche conductrice de semi-conducteur disposée sur la couche active. Ladite diode électroluminescente émettant dans l'ultraviolet satisfait à une expression relationnelle telle que 0 < y < 0,5, 0 < x < y, et y = -5 x + (0,5~0,7).
PCT/KR2015/011997 2015-02-06 2015-11-09 Diode électroluminescente émettant dans l'ultraviolet WO2016125993A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2015-0018375 2015-02-06
KR20150018375 2015-02-06
KR1020150031807A KR20160097098A (ko) 2015-02-06 2015-03-06 자외선 발광 다이오드
KR10-2015-0031807 2015-03-06

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WO2016125993A1 true WO2016125993A1 (fr) 2016-08-11

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109888068A (zh) * 2019-01-23 2019-06-14 华灿光电（浙江）有限公司 近紫外发光二极管外延片及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3796065B2 (ja) * 1999-05-24 2006-07-12 三洋電機株式会社 発光素子及びその製造方法
JP2007294877A (ja) * 2006-03-31 2007-11-08 Fujifilm Corp 半導体層とその成膜方法、及び半導体発光素子
JP2009049422A (ja) * 1999-11-16 2009-03-05 Panasonic Corp 相分離が抑制されたｉｉｉ族窒化物材料系を用いた半導体構造及び光検出器
US20130026482A1 (en) * 2011-07-29 2013-01-31 Bridgelux, Inc. Boron-Containing Buffer Layer for Growing Gallium Nitride on Silicon
US20130270519A1 (en) * 2012-04-16 2013-10-17 Sensor Electronic Technology, Inc. Non-Uniform Multiple Quantum Well Structure

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3796065B2 (ja) * 1999-05-24 2006-07-12 三洋電機株式会社 発光素子及びその製造方法
JP2009049422A (ja) * 1999-11-16 2009-03-05 Panasonic Corp 相分離が抑制されたｉｉｉ族窒化物材料系を用いた半導体構造及び光検出器
JP2007294877A (ja) * 2006-03-31 2007-11-08 Fujifilm Corp 半導体層とその成膜方法、及び半導体発光素子
US20130026482A1 (en) * 2011-07-29 2013-01-31 Bridgelux, Inc. Boron-Containing Buffer Layer for Growing Gallium Nitride on Silicon
US20130270519A1 (en) * 2012-04-16 2013-10-17 Sensor Electronic Technology, Inc. Non-Uniform Multiple Quantum Well Structure

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109888068A (zh) * 2019-01-23 2019-06-14 华灿光电（浙江）有限公司 近紫外发光二极管外延片及其制备方法
CN109888068B (zh) * 2019-01-23 2020-04-14 华灿光电（浙江）有限公司 近紫外发光二极管外延片及其制备方法

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