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WO2017188578A1 - Ultraviolet light emitting device transparent electrode and manufacturing method therefor - Google Patents

Ultraviolet light emitting device transparent electrode and manufacturing method therefor Download PDF

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Publication number
WO2017188578A1
WO2017188578A1 PCT/KR2017/001787 KR2017001787W WO2017188578A1 WO 2017188578 A1 WO2017188578 A1 WO 2017188578A1 KR 2017001787 W KR2017001787 W KR 2017001787W WO 2017188578 A1 WO2017188578 A1 WO 2017188578A1
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Prior art keywords
layer
light emitting
transparent electrode
fto
emitting device
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PCT/KR2017/001787
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French (fr)
Korean (ko)
Inventor
김경국
정종열
김동준
연규재
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Industry Academic Cooperation Foundation of Korea Polytechnic University
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Industry Academic Cooperation Foundation of Korea Polytechnic University
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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]
    • H10H20/01—Manufacture or treatment
    • 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
    • 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
    • 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
    • H10H20/83—Electrodes
    • H10H20/832—Electrodes characterised by their material
    • H10H20/833—Transparent materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/12—Passive devices, e.g. 2 terminal devices
    • H01L2924/1204—Optical Diode
    • H01L2924/12041—LED
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/01—Manufacture or treatment
    • H10H20/032—Manufacture or treatment of electrodes

Definitions

  • the present invention relates to a transparent electrode for an ultraviolet light emitting device, a manufacturing method thereof, and an ultraviolet light emitting device including the transparent electrode.
  • a light emitting diode has a heterojunction structure of a p-type semiconductor and an n-type semiconductor using a semiconductor compound, and when voltage is applied, electrons and holes combine to emit energy corresponding to the semiconductor band gap in the form of light. It is a kind of optoelectronic device.
  • UV-LEDs Light emitting diodes have been applied to displays, lighting, solar cells, etc., and recently, for UV-LEDs that generate light in the ultraviolet region, which is expected to be applied to various fields such as medical industry, bio industry, environmental industry, agriculture and fisheries industry, and defense industry. Research is active.
  • UV-LED has the advantage of low cost and high efficiency irradiation characteristics compared to existing light sources manufactured using special gas that is expensive and harmful to human body.
  • UV-LED has a high transmittance and high conductivity for ultraviolet region. Since development is required and expensive manufacturing methods such as flip-chip structures are applied to improve the efficiency of the UV-LED, economical manufacturing cost is required for commercialization.
  • UV-LED can propose an epi-up structure to reduce manufacturing cost, but ITO electrode (Transparent Conductive Oxide) is used as a transparent electrode applied to epi-up, and ITO electrode is applied to UV-LED.
  • ITO electrode Transparent Conductive Oxide
  • the light in the ultraviolet region (less than 400 nm) generated in the active layer is mostly absorbed or reflected by the ITO electrode, and the light extracted through the ITO electrode to be extracted to the outside rapidly decreases.
  • an ITO electrode using ITO / Ga 2 O 3 / glass has been proposed, but there is a problem in that the transmittance in the ultraviolet region is not satisfactory and the electrical characteristics are remarkably inferior.
  • an ITO electrode having a rough surface formed by surface-treating the ITO electrode has been presented.
  • UV transmittance is improved to some extent through the curved surface, an additional process is required, and thus, a manufacturing process is complicated.
  • the present invention is to solve the above problems, to provide a transparent electrode for an ultraviolet light emitting device having a high transmittance for the short wavelength region.
  • the present invention also provides a method for manufacturing the transparent electrode for ultraviolet light emitting device.
  • the present invention also provides an ultraviolet light emitting device comprising the transparent electrode for ultraviolet light emitting devices.
  • At least one of the first oxide layer and the second oxide layer relates to a transparent electrode for an ultraviolet light emitting device including fluorine doped tin oxide (FTO).
  • FTO fluorine doped tin oxide
  • At least one of the first oxide and the second oxide layer including the FTO may be an FTO-ITO mixed layer further comprising ITO.
  • the molar ratio of FTO: ITO in the mixed layer may vary from 1: 1 to 1: 5.
  • the first oxide layer / second oxide layer ITO / FT0; ITO / FTO-ITO; FTO / ITO; FTO / FTO; FTO / FTO-ITO; FTO-ITO / ITO; FTO-ITO / FTO; Or FTO-ITO / FTO-ITO; Can be.
  • the first oxide layer and the second oxide layer may each have a thickness from 10 nm to 100 nm.
  • the metal layer Ag, Au, Pd, Al, Pt, Cu, Zn, Cd, In, Si, Zr, Mo, Ni, Cr, Mg, Mn, Co and Sn It may include one or more selected from the group.
  • the metal layer may have a thickness of 1 nm to 50 nm.
  • the transparent electrode may have a light transmittance of 85% or more at a wavelength of 350 nm or less.
  • It relates to an ultraviolet light emitting device comprising the transparent electrode according to the present invention.
  • the light emitting device includes a semiconductor layer; A transparent electrode layer formed on at least one surface of the semiconductor layer; An electrode formed on at least a portion of the transparent electrode layer; It may include.
  • a buffer layer may be further included between the semiconductor layer and the transparent electrode layer.
  • the buffer layer may include a III-V-based semiconductor compound, a II-VI-based semiconductor compound, or both.
  • the semiconductor layer may include a first semiconductor layer; A second semiconductor layer; And an active layer between the first semiconductor layer and the second semiconductor layer.
  • the active layer may include a quantum structure.
  • first oxide layer on the semiconductor layer; Forming a metal layer on the first oxide layer; And forming a second oxide layer on the metal layer. And at least one of the first oxide layer and the second oxide layer relates to a method of manufacturing a transparent electrode for an ultraviolet light emitting device including FTO.
  • At least one of the first oxide and the second oxide layer including the FTO may be an FTO-ITO mixed layer further comprising ITO.
  • the forming of the mixed layer may be performed through coasting.
  • the manufacturing method may further include a heat treatment after forming the second oxide layer, and the heat treatment may be performed at 100 ° C. or higher.
  • the heat treatment may be heat treatment for 1 minute to 1 hour.
  • the present invention can provide a wide bandgap transparent electrode for a short wavelength ultraviolet light emitting device, which has high transmittance for UV-A and UV-B regions.
  • the present invention by applying the transparent electrode can lower the efficiency and manufacturing cost of the ultraviolet light emitting device.
  • the present invention can provide an ultraviolet light emitting device having a high brightness for the ultraviolet region.
  • FIG. 1 illustrates a cross-sectional view of a transparent electrode for an ultraviolet light emitting device according to an embodiment of the present invention.
  • FIG. 2 is a flowchart illustrating a method of manufacturing a transparent electrode for an ultraviolet light emitting device according to an embodiment of the present invention.
  • FIG. 3 is a cross-sectional view of an ultraviolet light emitting device including the transparent electrode for ultraviolet light emitting device of the present invention according to an embodiment of the present invention by way of example.
  • 4A to 4C show SEM images of surfaces of transparent electrodes for ultraviolet light emitting devices manufactured in Examples 1 to 3 of the present invention.
  • Figure 5 shows the light transmittance of the transparent electrode for ultraviolet light emitting device manufactured in Examples 1 to 3 of the present invention.
  • Figure 6 shows the light transmittance of the transparent electrode for ultraviolet light emitting device prepared in Examples 3 to 4 and Comparative Example 1 of the present invention.
  • the present invention relates to a transparent electrode for an ultraviolet light emitting device, the transparent electrode for an ultraviolet light emitting device according to an embodiment of the present invention, provides a stable transparent electrode characteristics based on a multi-component oxide, UV-A and A wide bandgap transparent electrode exhibiting high transmittance in the UV-B region can be provided.
  • a transparent electrode for an ultraviolet light emitting device will be described with reference to Figure 1,
  • Figure 1 is a transparent electrode for ultraviolet light emitting device 20 according to an embodiment of the present invention Exemplary cross-sectional views are shown.
  • the transparent electrode 20 for UV light emitting devices may include a first oxide layer 21, a metal layer 22, and a second oxide layer 23.
  • the first oxide layer 21 may provide good ohmic contact characteristics with the semiconductor layer of the light emitting device, and may provide high transparency to a short wavelength region.
  • the first oxide layer 21 is formed on the semiconductor layer 10 and is formed of FTO fluorine doped tin oxide; Indium Tin Oxide (ITO); Or it may include both, and may preferably include a FTO or FTO-ITO mixed layer.
  • the FTO-ITO mixed layer may have a molar ratio of FTO to ITO of 1: 1 to 1: 5; More preferably, 1: 1 to 1: 2 may be mixed, and when included in the molar ratio, it may exhibit high permeability to a short wavelength region.
  • the first oxide layer 21 may be 10 nm to 100 nm, preferably 10 nm to 70 nm; More preferably, it may have a thickness of 10 nm to 50 nm, and when included in the thickness range, the semiconductor layer and the ohmic contact may be well made while exhibiting high transparency to the short wavelength region.
  • the metal layer 22 is to provide a high electrical conductivity, for example, Ag, Au, Pd, Al, Pt, Cu, Zn, Cd, In, Si, Zr, Mo, Ni, It may include one or more selected from the group consisting of Cr, Mg, Mn, Co, and Sn, preferably Ag.
  • the metal layer 22 may have a thickness of 1 nm to 50 nm, preferably 1 to 20 nm, and when included in the thickness range, transmittance at a specific range of wavelengths may be improved by surface plasmon effect. Can be.
  • the second oxide layer 23 may include an oxide having the same component as or different from that of the first oxide layer 21, and may include, for example, FTO; ITO; Or both, provided that the first oxide layer 21 / second oxide layer 23 is not composed of ITO / ITO.
  • at least one of the first oxide layer 21 and the second oxide layer 23 may include FTO, and at least one of the oxide layers including FTO may further include ITO.
  • the first oxide layer 21 / the second oxide layer 23 may include ITO / FT0; ITO / FTO-ITO; FTO / ITO; FTO / FTO; FTO / FTO-ITO; FTO-ITO / ITO; FTO-ITO / FTO; Or FTO-ITO / FTO-ITO; Can be.
  • the second oxide layer 23 may have the same or different thickness as the first oxide layer 21, and the second oxide layer 23 may include 10 nm to 100 nm; Preferably 10 nm to 70 nm; More preferably, it may have a thickness of 10 nm to 50 nm.
  • the transparent electrode for ultraviolet light emitting device 50% or more in the wavelength region of 360 nm or less; Preferably it can exhibit a light transmittance of 85% or more.
  • the present invention provides a method for manufacturing a transparent electrode for an ultraviolet light emitting device according to the present invention.
  • the manufacturing method provides a transparent electrode having a high transmittance for a short wavelength region, When the manufacturing method is applied to the manufacturing method of the ultraviolet light emitting device can reduce the manufacturing cost of the light emitting device.
  • FIG. 2 is a method of manufacturing a transparent electrode for an ultraviolet light emitting device according to an embodiment of the present invention.
  • the manufacturing method of FIG. 2 includes preparing a semiconductor layer (S1), forming a first oxide layer (S2), forming a metal layer (S3), and The method may include forming a second oxide layer (S4), and may further include performing a heat treatment (S5).
  • preparing the semiconductor layer (S1) is a step of preparing the semiconductor layer 10 for the light generation of the ultraviolet light emitting device
  • any semiconductor layer applicable to the ultraviolet light emitting device can be applied without limitation
  • the semiconductor layer may include a gallium nitride-based semiconductor light emitting diode, and may include an n-type semiconductor layer, an active layer, and a p-type semiconductor layer, but will be described in more detail with reference to the following light emitting devices. .
  • the preparing of the semiconductor layer (S1) may use a method applied in the technical field of the present invention, for example, chemical vapor deposition (CVD), physical vapor deposition (PVD), or MOCVD (metal).
  • the semiconductor layer may be formed using a gas phase growth method such as organic chemical vapor deposition (MPE), molecular beam epitaxy (MBE), or hydraulic vapor phase epitaxy (HVPE), but is not limited thereto.
  • MPE organic chemical vapor deposition
  • MBE molecular beam epitaxy
  • HVPE hydraulic vapor phase epitaxy
  • the forming of the first oxide layer (S2) is a step of forming the first oxide layer 21 on the semiconductor layer 10.
  • the first oxide layer 21 is composed of the components as shown in the transparent electrode.
  • the step (S2) of forming the first oxide layer may include sputtering, such as direct current magnetron sputtering, radio frequency magnetron sputtering, chemical vapor deposition (CVD), thermal chemical vapor deposition (TCVD), and microwave plasma chemical vapor deposition. (MPECVD), a solution vapor deposition method, or the like can be used.
  • sputtering such as direct current magnetron sputtering, radio frequency magnetron sputtering, chemical vapor deposition (CVD), thermal chemical vapor deposition (TCVD), and microwave plasma chemical vapor deposition. (MPECVD), a solution vapor deposition method, or the like can be used.
  • the first oxide layer 21 can be formed by sputtering.
  • the sputtering target may use an oxide target or a metal target, use an inert gas such as argon, helium, neon gas, or the like as the sputter gas, and use an oxidizing gas such as oxygen or carbon dioxide as the sputter gas. Further oxidizing gas can be used with up to 10% of the sputter gas.
  • the sputtering method is introduced at an argon gas flow rate of 10 to 20 sccm and an oxygen flow rate of 1 to 2 sccm, at a temperature of 25 ° C. ⁇ 5 ° C.
  • each component may be coped to form the first oxide layer, for example, the first oxide layer may be FTO.
  • FTO and ITO may be formed by co-sputtering at the same time.
  • the forming of the metal layer (S3) is a step of forming the metal layer 22 on the first oxide layer 21.
  • Step S3 of forming the metal layer may be performed using a sputtering method or the like, and may be formed in the same manner as step S2.
  • the forming of the second oxide layer (S4) is a step of forming the second oxide layer 23 on the metal layer 22.
  • the step (S4) of forming the second oxide layer may include sputtering such as direct current magnetron sputtering, radio frequency magnetron sputtering, chemical vapor deposition (CVD), thermal chemical vapor deposition (TCVD), or microwave plasma chemical vapor deposition (MPECVD). , A solution deposition method, or the like may be used.
  • the second oxide layer 23 may be formed using a sputtering method, and may be performed in the same manner as in step S2.
  • the method for manufacturing a transparent electrode may further include a step (S5) of heat treatment.
  • a step (S5) of heat treatment after the formation of the second oxide layer, oxidation of the first and second oxide layers is performed to stabilize the oxides, and to secure electrical characteristics through recrystallization of the internal crystal system, Increasing the spacing between grains can increase the transparency of the transparent electrode.
  • the heat treatment temperature in the step (S5) of the heat treatment may be 100 °C or more, in order to prevent a decrease in the optical transmittance due to the irregular shape of the oxide layer particles due to the heat treatment, preferably 200 °C to 800 °C, more Preferably from 300 ° C to 700 ° C, more preferably from 500 ° C to 700 ° C.
  • the heat treatment step (S5) may be heat treated for 1 minute to 1 hour in an air atmosphere, preferably 1 minute to 30 minutes; More preferably, it may be 1 to 15 minutes. When the heat treatment time is included in the above range, oxidation proceeds smoothly, and a decrease in transmittance of the ultraviolet region due to excessive heat treatment may be prevented.
  • the present invention relates to an ultraviolet light emitting device, according to an embodiment of the present invention, the ultraviolet light emitting device, by applying a transparent electrode according to the present invention to improve the low transmittance of the ultraviolet region according to the conventional ITO electrode by ultraviolet light It can represent high brightness for the region.
  • the ultraviolet light emitting device can be manufactured in a vertical or horizontal epi-side up structure can be improved economic efficiency.
  • the light emitting device will be described with reference to FIG. 3, and FIG. 3 is a cross-sectional view of an ultraviolet light emitting device according to an embodiment of the present invention.
  • the light emitting device may include a substrate 110, semiconductor layers 130, 140, and 150, a transparent electrode layer 160, and an electrode 170, and may further include a buffer layer 120.
  • the substrate 110 may be used without limitation as long as it is a substrate applicable to an ultraviolet light emitting device of the technical field of the present invention.
  • sapphire, diamond, InP, AlGaN, LiAlO 2 , InN, GaP , Ge, InAs, AlAs, SiO 2 , Si, SiC, GaN, GaAs and may include one or more selected from the group consisting of, but is not limited thereto.
  • the semiconductor layers 130, 140, and 150 may be formed on the substrate 110 and include the first semiconductor layer 130, the active layer 140, and the second semiconductor layer 150. have.
  • the first semiconductor layer 130 includes a wide bandgap semiconductor compound, for example, an III-V-based semiconductor compound, an II-VI-based semiconductor compound, or an N-type semiconductor compound including the two.
  • the III-V-based semiconductor compound is GaN, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, AlGaN, AlGaP, AlGaAs, AlGaSb, InGaN, GaInP, GaInAs, GaInSb , AlInN, AlInP, AlInAs, AlInSb, AlGaInN, AlGaInP, AlGaInAs and at least one selected from the group consisting of AlGaInSb, wherein the II-VI-based semiconductor compound, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, and It may include one or more selected from the group consisting of Cd
  • the active layer 140 is a region where light in the ultraviolet region is generated, and may include a single or multiple quantum well layer.
  • the second semiconductor layer 150 may be a III-V-based semiconductor compound, a II-VI-based semiconductor compound, or a p-type semiconductor compound including the two.
  • the III-V-based semiconductor compound is GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, AlGaN, AlGaP, AlGaAs, AlGaSb, InGaN, GaInP, GaInAs , GaInSb, AlInN, AlInP, AlInAs, AlInSb, AlGaInN, AlGaInP, AlGaInAs and at least one selected from the group consisting of AlGaInSb
  • the II-VI-based semiconductor compound is ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, And it may include one or more selected from the group consisting of CdTe.
  • the transparent electrode layer 160 forms ohmic contacts with the semiconductor compound layers 130, 140, and 150, and the transparent electrode layer 160 is formed in the short wavelength region of the light emitted from the active layer 140.
  • the transparent electrode layer 160 is formed in the short wavelength region of the light emitted from the active layer 140.
  • the electrode 170 may supply electric current to the light emitting device to enable electric driving.
  • the electrode 170 may include an N-type electrode 170a and a p-type electrode 170b.
  • the n-type metal electrode layer 170a is formed of Co, Ir, Ta, Cr, Mn, Mo, Tc, W, Re, Fe, Sc, Ti, Sn, Ge, Sb, Al, Pt, Ni, Au It may consist of a single layer or a plurality of layers, consisting of one or a mixture of two or more of, ITO and ZnO.
  • the p-type metal electrode layer 170b includes Co, Ir, Ta, Cr, Mn, Mo, Tc, W, Re, Fe, Sc, Ti, Sn, Ge, Sb, Al, Pt, Ni, Au It may consist of a single layer or a plurality of layers, consisting of one or a mixture of two or more of, ITO and ZnO.
  • the buffer layer 120 is for facilitating the growth of the first semiconductor layer 130 and includes an undoped semiconductor compound, for example, a III-V-based semiconductor compound, II- VI-based semiconductor compound or both may be included, wherein the semiconductor compound is as mentioned above.
  • an undoped semiconductor compound for example, a III-V-based semiconductor compound, II- VI-based semiconductor compound or both may be included, wherein the semiconductor compound is as mentioned above.
  • the ultraviolet light emitting device according to the present invention may further include a configuration of the ultraviolet light emitting device applied in the technical field of the present invention, without departing from the object of the present invention, for example, a transparent electrode layer (The current spreading layer may be further formed on the 160, but is not limited thereto.
  • a semiconductor layer having n-GnN / MQW formed on a sapphire substrate was prepared, and FTO-ITO (70 nm, FTO :) was formed on the semiconductor layer under sputtering gas (Ar), temperature (500 ° C.), and pressure (3 mTorr).
  • a UV-LED having a transparent electrode of ITO 1: 1) / Ag (14 nm) / FTO-ITO (70 nm) thin film was prepared. The SEM image of the surface of the transparent electrode was measured and shown in FIG. 4A, and the light transmittance was measured and shown in FIG. 5 using a UV-spectrometer apparatus.
  • UV-LEDs were manufactured in the same manner. The SEM image of the surface of the transparent electrode was measured and shown in FIG. 4B, and the light transmittance was measured and shown in FIG. 5 using a UV-spectrometer apparatus.
  • UV-LED was prepared in the same manner as in Example 1 using a transparent electrode of FTO (50 nm) / Ag (14 nm) / FTO (50 nm) thin film.
  • the UV-LED was heat treated at 500 ° C. for 1 minute.
  • the light transmittance was measured using a UV-spectrometer device and is shown in FIG. 6.
  • a UV-LED was manufactured and heat-treated in the same manner as in Example 3 except that a transparent electrode of an ITO (50 nm) / Ag (14 nm) / ITO (50 nm) thin film was formed.
  • the light transmittance was measured using a UV-spectrometer device and is shown in FIG. 6.
  • Example 4 to 6 in the transparent electrode of Example 2 having a thin oxide layer in FIGS. 4A, 4B, 4C, and 5, particle grains of the oxide layer are increased and transmittance in the ultraviolet region is performed. It can be seen that compared with Example 1.
  • the heat-treated transparent electrode Example 3 exhibited a significantly increased ultraviolet transmittance, which was improved by stabilization due to recrystallization of the oxide layer during heat treatment and improved grain permeability due to an increase in grain size of the oxide layer. Can be predicted.
  • Example 3 and Example 4 including the FTO according to the present invention, compared to the transparent electrode of the ITO-OMO (oxide / metal / oxide) structure of Comparative Example 1 UV of 360 nm or less It can be seen that it provides a significantly increased transmittance in the region. This shows that, when the oxide layer including the FTO according to the present invention is applied to a transparent electrode, the UV transmittance can be improved as compared with the conventional ITO-based transparent electrode.
  • the transparent electrode for an ultraviolet light emitting device to which the oxide layer including the FTO according to the present invention is applied can provide a high transmittance to a short wavelength ultraviolet region and improve the efficiency of the ultraviolet light emitting device.
  • the transparent electrode according to the present invention is applied to an ultraviolet light emitting device, it is possible to manufacture a horizontal or vertical ultraviolet light emitting device can lower the manufacturing cost compared to the ultraviolet light emitting device manufactured with a conventional flip chip structure. .

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Abstract

The present invention relates to an ultraviolet light emitting device transparent electrode and a manufacturing method therefor and, more specifically, to: an ultraviolet light emitting device transparent electrode comprising a first oxide layer, a metal layer formed on the first oxide layer, and a second oxide layer formed on the metal layer, wherein the first oxide layer and/or the second oxide layer comprises fluorine-doped tin oxide (FTO); and a manufacturing method therefor. The present invention can provide the ultraviolet light emitting device transparent electrode, which has high transmittance with respect to a short wavelength region, and reduce manufacturing costs of an ultraviolet light emitting device.

Description

자외선 발광소자용 투명전극 및 이의 제조방법Transparent electrode for ultraviolet light emitting device and manufacturing method thereof

본 발명은, 자외선 발광소자용 투명전극, 이의 제조방법 및 상기 투명전극을 포함하는 자외선 발광소자에 관한 것이다. The present invention relates to a transparent electrode for an ultraviolet light emitting device, a manufacturing method thereof, and an ultraviolet light emitting device including the transparent electrode.

발광 다이오드(Light Emittering Diode, LED)는 반도체 화합물을 이용한 p형 반도체와 n형 반도체의 이종접합구조를 가지며, 전압을 가하면 전자와 정공이 결합하여 반도체 밴드갭에 해당되는 에너지를 빛의 형태로 방출하는 광전자 소자의 한 종류이다.A light emitting diode (LED) has a heterojunction structure of a p-type semiconductor and an n-type semiconductor using a semiconductor compound, and when voltage is applied, electrons and holes combine to emit energy corresponding to the semiconductor band gap in the form of light. It is a kind of optoelectronic device.

발광 다이오드는, 디스플레이, 조명, 태양전지 등에 적용되고 있으며, 최근에는 의료산업, 바이오산업, 환경산업, 농수산업, 국방산업 등 다양한 분야에 적용이 기대되는 자외선 영역의 빛을 발생시키는 UV-LED에 대한 연구가 활발하게 진행되고 있다. Light emitting diodes have been applied to displays, lighting, solar cells, etc., and recently, for UV-LEDs that generate light in the ultraviolet region, which is expected to be applied to various fields such as medical industry, bio industry, environmental industry, agriculture and fisheries industry, and defense industry. Research is active.

UV-LED는, 고가 및 인체에 유해한 특수 가스를 이용하여 제조되는 기존 광원에 비해 가격이 낮고, 고효율의 조사 특성을 얻을 수 있는 장점이 있으나, 자외선 영역 대한 고투과도 및 고전도성을 갖는 투명전극의 개발이 필요하고, UV-LED의 효율을 향상시키기 위해 플립칩(Flip-Chip) 구조와 같은 고가의 제작방식이 적용되므로, 상용화를 위해서 경제적인 제조단가가 요구된다.UV-LED has the advantage of low cost and high efficiency irradiation characteristics compared to existing light sources manufactured using special gas that is expensive and harmful to human body. However, UV-LED has a high transmittance and high conductivity for ultraviolet region. Since development is required and expensive manufacturing methods such as flip-chip structures are applied to improve the efficiency of the UV-LED, economical manufacturing cost is required for commercialization.

일반적으로 UV-LED는 제조단가를 낮추기 위해 epi-up 구조를 제안할 수 있으나, epi-up에 적용되는 투명전극으로 ITO전극(Transparent Conductive Oxide)이 이용되고 있고, ITO전극이 UV-LED에 적용될 경우에, 활성층에서 생성된 자외선 영역(400 nm 미만)의 빛이 대부분 ITO 전극에 흡수되거나 반사되어 ITO 전극을 투과하여 외부로 추출되는 빛이 급격하게 낮아진다. In general, UV-LED can propose an epi-up structure to reduce manufacturing cost, but ITO electrode (Transparent Conductive Oxide) is used as a transparent electrode applied to epi-up, and ITO electrode is applied to UV-LED. In this case, the light in the ultraviolet region (less than 400 nm) generated in the active layer is mostly absorbed or reflected by the ITO electrode, and the light extracted through the ITO electrode to be extracted to the outside rapidly decreases.

이러한 문제점을 해결하기 위해서, 예를 들어, ITO/Ga2O3 /glass를 이용한 ITO 전극이 제안되었으나, 자외선 영역에 대한 투과도가 만족스럽지 않고, 전기적 특성이 현저하게 떨어지는 문제점이 있다. 또한, ITO 전극을 표면 처리하여 굴곡표면(rough surface)이 형성된 ITO 전극이 제시되었으나, 굴곡표면을 통하여 자외선 투과도는 어느 정도 향상되었으나, 추가 공정이 더 필요하므로, 제조공정이 복잡해지는 문제점이 있다.In order to solve this problem, for example, an ITO electrode using ITO / Ga 2 O 3 / glass has been proposed, but there is a problem in that the transmittance in the ultraviolet region is not satisfactory and the electrical characteristics are remarkably inferior. In addition, an ITO electrode having a rough surface formed by surface-treating the ITO electrode has been presented. However, although UV transmittance is improved to some extent through the curved surface, an additional process is required, and thus, a manufacturing process is complicated.

본 발명은 전술한 바와 같은 문제점을 해결하기 위한 것으로, 단파장 영역에 대한 높은 투과율을 갖는 자외선 발광소자용 투명전극을 제공하는 것이다.The present invention is to solve the above problems, to provide a transparent electrode for an ultraviolet light emitting device having a high transmittance for the short wavelength region.

또한, 본 발명은, 상기 자외선 발광소자용 투명전극의 제조방법을 제공하는 것이다.The present invention also provides a method for manufacturing the transparent electrode for ultraviolet light emitting device.

또한, 본 발명은, 상기 자외선 발광소자용 투명전극을 포함하는 자외선 발광소자를 제공하는 것이다. The present invention also provides an ultraviolet light emitting device comprising the transparent electrode for ultraviolet light emitting devices.

본 발명이 해결하고자 하는 과제는 이상에서 언급한 과제로 제한되지 않으며, 언급되지 않은 또 다른 과제들은 아래의 기재로부터 통상의 기술자에게 명확하게 이해될 수 있을 것이다.The problem to be solved by the present invention is not limited to the above-mentioned problem, another task that is not mentioned will be clearly understood by those skilled in the art from the following description.

본 발명의 하나의 양상은, One aspect of the present invention,

제1 산화물층; 상기 제1 산화물층 상에 형성된 금속층; 및 상기 금속층 상에 형성된 제2 산화물층; 을 포함하고, A first oxide layer; A metal layer formed on the first oxide layer; And a second oxide layer formed on the metal layer. Including,

상기 제1 산화물층 및 제2 산화물층 중 적어도 어느 하나는, FTO(fluorine doped tin oxide)를 포함하는 자외선 발광소자용 투명전극에 관한 것이다. At least one of the first oxide layer and the second oxide layer relates to a transparent electrode for an ultraviolet light emitting device including fluorine doped tin oxide (FTO).

본 발명의 일 실시예에 따라, 상기 FTO를 포함하는 상기 제1 산화물 및 제2 산화물층 중 적어도 어느 하나는 ITO를 더 포함하는 FTO-ITO 혼합층일 수 있다.According to an embodiment of the present invention, at least one of the first oxide and the second oxide layer including the FTO may be an FTO-ITO mixed layer further comprising ITO.

본 발명의 일 실시예에 따라, 상기 혼합층 중 FTO:ITO 몰비는 1:1에서 1:5까지 변화할 수 있다.According to one embodiment of the present invention, the molar ratio of FTO: ITO in the mixed layer may vary from 1: 1 to 1: 5.

본 발명의 일 실시예에 따라, 상기 제1 산화물층/제2 산화물층은, ITO/FT0; ITO/FTO-ITO; FTO/ITO; FTO/FTO; FTO/FTO-ITO; FTO-ITO/ITO; FTO-ITO/FTO; 또는 FTO-ITO/FTO-ITO; 일 수 있다.According to one embodiment of the invention, the first oxide layer / second oxide layer, ITO / FT0; ITO / FTO-ITO; FTO / ITO; FTO / FTO; FTO / FTO-ITO; FTO-ITO / ITO; FTO-ITO / FTO; Or FTO-ITO / FTO-ITO; Can be.

본 발명의 일 실시예에 따라, 상기 제1 산화물층 및 제2 산화물층은 각각, 10 nm에서 100 nm까지 두께를 갖는 것일 수 있다. According to one embodiment of the present invention, the first oxide layer and the second oxide layer may each have a thickness from 10 nm to 100 nm.

본 발명의 일 실시예에 따라, 상기 금속층은, Ag, Au, Pd, Al, Pt, Cu, Zn, Cd, In, Si, Zr, Mo, Ni, Cr, Mg, Mn, Co 및 Sn으로 이루어진 군에서 선택된 1종 이상을 포함할 수 있다.According to one embodiment of the invention, the metal layer, Ag, Au, Pd, Al, Pt, Cu, Zn, Cd, In, Si, Zr, Mo, Ni, Cr, Mg, Mn, Co and Sn It may include one or more selected from the group.

본 발명의 일 실시예에 따라, 상기 금속층은, 1 nm 내지 50 nm 두께을 가질 수 있다.According to one embodiment of the invention, the metal layer may have a thickness of 1 nm to 50 nm.

본 발명의 일 실시예에 따라, 상기 투명전극은 350 nm 이하의 파장에서 광투과율이 85 % 이상일 수 있다.According to an embodiment of the present invention, the transparent electrode may have a light transmittance of 85% or more at a wavelength of 350 nm or less.

본 발명의 다른 양상은,Another aspect of the invention,

본 발명에 의한 투명전극을 포함하는, 자외선 발광소자에 관한 것이다.It relates to an ultraviolet light emitting device comprising the transparent electrode according to the present invention.

본 발명의 일 실시예에 따라, 상기 발광소자는, 반도체층; 상기 반도체층의 적어도 일면에 형성된 투명전극층; 및 상기 투명전극층의 적어도 일부분에 형성된 전극; 을 포함할 수 있다.According to an embodiment of the present invention, the light emitting device includes a semiconductor layer; A transparent electrode layer formed on at least one surface of the semiconductor layer; An electrode formed on at least a portion of the transparent electrode layer; It may include.

본 발명의 일 실시예에 따라, 상기 반도체층 및 상기 투명전극층 사이에 버퍼층을 더 포함할 수 있다.According to an embodiment of the present invention, a buffer layer may be further included between the semiconductor layer and the transparent electrode layer.

본 발명의 일 실시예에 따라, 상기 버퍼층은, III-V계 반도체 화합물, II-VI계 반도체 화합물 또는 이 둘을 포함할 수 있다.According to an embodiment of the present invention, the buffer layer may include a III-V-based semiconductor compound, a II-VI-based semiconductor compound, or both.

본 발명의 일 실시예에 따라, 상기 반도체층은, 제1 반도체층; 제2 반도체층; 및 상기 제1 반도체층 및 상기 제2 반도체층 사이에 활성층을 포함할 수 있다.According to an embodiment of the present invention, the semiconductor layer may include a first semiconductor layer; A second semiconductor layer; And an active layer between the first semiconductor layer and the second semiconductor layer.

본 발명의 일 실시예에 따라, 상기 활성층은, 양자구조를 포함할 수 있다.According to an embodiment of the present invention, the active layer may include a quantum structure.

본 발명의 또 다른 양상은, Another aspect of the invention,

반도체층 상에 제1 산화물층을 형성하는 단계; 상기 제1 산화물층 상에 금속층을 형성하는 단계; 및 상기 금속층 상에 제2 산화물층을 형성하는 단계; 를 포함하고, 상기 제1 산화물층 및 제2 산화물층 중 적어도 어느 하나는, FTO를 포함하는 자외선 발광소자용 투명전극의 제조방법에 관한 것이다.Forming a first oxide layer on the semiconductor layer; Forming a metal layer on the first oxide layer; And forming a second oxide layer on the metal layer. And at least one of the first oxide layer and the second oxide layer relates to a method of manufacturing a transparent electrode for an ultraviolet light emitting device including FTO.

본 발명의 일 실시예에 따라, 상기 FTO를 포함하는 상기 제1 산화물 및 제2 산화물층 중 적어도 어느 하나는 ITO를 더 포함하는 FTO-ITO 혼합층일 수 있다.According to an embodiment of the present invention, at least one of the first oxide and the second oxide layer including the FTO may be an FTO-ITO mixed layer further comprising ITO.

본 발명의 일 실시예에 따라, 상기 혼합층을 형성하는 단계는 코스퍼터링을 통해 수행할 수 있다. According to an embodiment of the present invention, the forming of the mixed layer may be performed through coasting.

본 발명의 일 실시예에 따라, 상기 제조방법은, 제2 산화물층을 형성하는 단계 이후에 열처리하는 단계를 더 포함하고, 상기 열처리하는 단계는, 100 ℃ 이상에서 수행할 수 있다.According to an embodiment of the present invention, the manufacturing method may further include a heat treatment after forming the second oxide layer, and the heat treatment may be performed at 100 ° C. or higher.

본 발명의 일 실시예에 따라, 상기 열처리하는 단계는, 1분 내지 1시간동안 열처리할 수 있다.According to an embodiment of the present invention, the heat treatment may be heat treatment for 1 minute to 1 hour.

본 발명은, UV-A와 UV-B영역에 대한 높은 투과도를 갖는, 단파장 자외선 발광소자용 와이드 밴드갭 투명전극을 제공할 수 있다.The present invention can provide a wide bandgap transparent electrode for a short wavelength ultraviolet light emitting device, which has high transmittance for UV-A and UV-B regions.

또한, 본 발명은, 상기 투명전극을 적용하여 자외선 발광소자의 효율과 제조단가를 낮출 수 있다.In addition, the present invention, by applying the transparent electrode can lower the efficiency and manufacturing cost of the ultraviolet light emitting device.

또한, 본 발명은, 자외선 영역에 대한 고휘도를 갖는 자외선 발광소자를 제공할 수 있다.In addition, the present invention can provide an ultraviolet light emitting device having a high brightness for the ultraviolet region.

도 1은, 본 발명의 일 실시예에 따른, 본 발명의 자외선 발광소자용 투명전극에 대한 단면도를 예시적으로 나타낸 것이다.1 illustrates a cross-sectional view of a transparent electrode for an ultraviolet light emitting device according to an embodiment of the present invention.

도 2는, 본 발명의 일 실시예에 따른, 본 발명의 자외선 발광소자용 투명전극의 제조방법에 대한 흐름도를 예시적으로 나타낸 것이다.2 is a flowchart illustrating a method of manufacturing a transparent electrode for an ultraviolet light emitting device according to an embodiment of the present invention.

도 3은, 본 발명의 일 실시예에 따른, 본 발명의 자외선 발광소자용 투명전극을 포함하는 자외선 발광소자의 단면도를 예시적으로 나타낸 것이다.3 is a cross-sectional view of an ultraviolet light emitting device including the transparent electrode for ultraviolet light emitting device of the present invention according to an embodiment of the present invention by way of example.

도 4a 내지 4c는, 본 발명의 실시예 1 내지 실시예 3에서 제조된 자외선 발광소자용 투명전극의 표면에 대한 SEM 이미지를 나타낸 것이다.4A to 4C show SEM images of surfaces of transparent electrodes for ultraviolet light emitting devices manufactured in Examples 1 to 3 of the present invention.

도 5는, 본 발명의 실시예 1 내지 실시예 3에서 제조된 자외선 발광소자용 투명전극의 광투과도를 나타낸 것이다.Figure 5 shows the light transmittance of the transparent electrode for ultraviolet light emitting device manufactured in Examples 1 to 3 of the present invention.

도 6은, 본 발명의 실시예 3 내지 실시예 4 및 비교예 1에서 제조된 자외선 발광소자용 투명전극의 광투과도를 나타낸 것이다.Figure 6 shows the light transmittance of the transparent electrode for ultraviolet light emitting device prepared in Examples 3 to 4 and Comparative Example 1 of the present invention.

이하 첨부된 도면을 참조하여 본 발명의 실시예들을 상세히 설명한다. 본 발명을 설명함에 있어서, 관련된 공지 기능 또는 구성에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명을 생략할 것이다. 또한, 본 명세서에서 사용되는 용어(terminology)들은 본 발명의 바람직한 실시예를 적절히 표현하기 위해 사용된 용어들로, 이는 사용자, 운용자의 의도 또는 본 발명이 속하는 분야의 관례 등에 따라 달라질 수 있다. 따라서, 본 용어들에 대한 정의는 본 명세서 전반에 걸친 내용을 토대로 내려져야 할 것이다. 각 도면에 제시된 동일한 참조 부호는 동일한 부재를 나타낸다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. In describing the present invention, when it is determined that detailed descriptions of related known functions or configurations may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted. In addition, terms used herein are terms used to properly express preferred embodiments of the present invention, which may vary depending on the intention of a user, an operator, or customs in the field to which the present invention belongs. Therefore, the definitions of the terms should be made based on the contents throughout the specification. Like reference numerals in the drawings denote like elements.

본 발명은, 자외선 발광소자용 투명전극에 관한 것으로, 본 발명의 일 실시예에 따른, 자외선 발광소자용 투명전극은, 다성분계 산화물을 바탕으로 하여 안정적인 투명전극 특성을 제공하고, UV-A와 UV-B 영역에서 높은 투과율을 나타내는 와이드 밴드갭 투명전극을 제공할 수 있다. The present invention relates to a transparent electrode for an ultraviolet light emitting device, the transparent electrode for an ultraviolet light emitting device according to an embodiment of the present invention, provides a stable transparent electrode characteristics based on a multi-component oxide, UV-A and A wide bandgap transparent electrode exhibiting high transmittance in the UV-B region can be provided.

본 발명의 일 실시예에 따라, 본 발명에 의한 자외선 발광소자용 투명전극은 도 1을 참조하여 설명하며, 도 1은 본 발명의 일 실시예에 따른 자외선 발광소자용 투명전극(20)에 대한 단면도를 예시적으로 나타낸 것이다. 도 1에서 상기 자외선 발광소자용 투명전극(20)은, 제1 산화물층(21), 금속층(22) 및 제2 산화물층(23)을 포함할 수 있다. According to one embodiment of the invention, a transparent electrode for an ultraviolet light emitting device according to the present invention will be described with reference to Figure 1, Figure 1 is a transparent electrode for ultraviolet light emitting device 20 according to an embodiment of the present invention Exemplary cross-sectional views are shown. In FIG. 1, the transparent electrode 20 for UV light emitting devices may include a first oxide layer 21, a metal layer 22, and a second oxide layer 23.

본 발명의 일 예로, 제1 산화물층(21)은, 발광소자의 반도체층과 양호한 오믹 콘택 특성을 제공하고, 단파장 영역에 대한 고투과성을 제공할 수 있다. As an example of the present invention, the first oxide layer 21 may provide good ohmic contact characteristics with the semiconductor layer of the light emitting device, and may provide high transparency to a short wavelength region.

예를 들어, 제1 산화물층(21)은, 반도체층(10) 상에 형성되고, FTO fluorine doped tin oxide); ITO(Indium Tin Oxide); 또는 이 둘을 포함할 수 있으며, 바람직하게는 FTO 또는 FTO-ITO 혼합층을 포함할 수 있다. 예를 들어, FTO-ITO 혼합층은, FTO 대 ITO가 1:1 내지 1:5의 몰비; 더 바람직하게는 1:1: 내지 1:2로 혼합될 수 있으며, 상기 몰비 내로 포함되면 단파장 영역에 대한 고투과성을 나타낼 수 있다. For example, the first oxide layer 21 is formed on the semiconductor layer 10 and is formed of FTO fluorine doped tin oxide; Indium Tin Oxide (ITO); Or it may include both, and may preferably include a FTO or FTO-ITO mixed layer. For example, the FTO-ITO mixed layer may have a molar ratio of FTO to ITO of 1: 1 to 1: 5; More preferably, 1: 1 to 1: 2 may be mixed, and when included in the molar ratio, it may exhibit high permeability to a short wavelength region.

예를 들어, 제1 산화물층(21)은, 10 nm 내지 100 nm, 바람직하게는 10 nm 내지 70 nm; 더 바람직하게는 10 nm 내지 50 nm의 두께를 가질 수 있으며, 상기 두께 범위 내에 포함되면, 단파장 영역에 대한 고투과성을 나타내면서 반도체층과 오믹 컨택이 잘 이루어질 수 있다.  For example, the first oxide layer 21 may be 10 nm to 100 nm, preferably 10 nm to 70 nm; More preferably, it may have a thickness of 10 nm to 50 nm, and when included in the thickness range, the semiconductor layer and the ohmic contact may be well made while exhibiting high transparency to the short wavelength region.

본 발명의 일 예로, 금속층(22)은, 높은 전기 전도성을 제공하는 것으로, 예를 들어, Ag, Au, Pd, Al, Pt, Cu, Zn, Cd, In, Si, Zr, Mo, Ni, Cr, Mg, Mn, Co 및 Sn으로 이루어진 군에서 선택된 1종 이상을 포함할 수 있고, 바람직하게는 Ag를 포함할 수 있다. 예를 들어, 금속층(22)은, 1 nm 내지 50 nm 두께, 바람직하게는 1 내지 20 nm 두께를 가질 수 있고, 상기 두께 범위 내에 포함되면 표면 플라즈몬 효과에 의해 특정 범위의 파장에서 투과율을 향상시킬 수 있다. In one embodiment of the present invention, the metal layer 22 is to provide a high electrical conductivity, for example, Ag, Au, Pd, Al, Pt, Cu, Zn, Cd, In, Si, Zr, Mo, Ni, It may include one or more selected from the group consisting of Cr, Mg, Mn, Co, and Sn, preferably Ag. For example, the metal layer 22 may have a thickness of 1 nm to 50 nm, preferably 1 to 20 nm, and when included in the thickness range, transmittance at a specific range of wavelengths may be improved by surface plasmon effect. Can be.

본 발명의 일 예로, 제2 산화물층(23)은, 제1 산화물층(21)과 동일한 성분 또는 상이한 성분의 산화물을 포함할 수 있고, 예를 들어, FTO; ITO; 또는 이 둘을 포함할 수 있고, 단, 제1 산화물층(21)/제2 산화물층(23)이 ITO/ITO로 구성되지 않는다. 예를 들어, 제1 산화물층(21) 및 제2 산화물층(23) 중 적어도 하나는 FTO를 포함할 수 있고, FTO를 포함하는 산화물층 중 적어도 하나는 ITO를 더 포함할 수 있다. 예를 들어, 제1 산화물층(21)/제2 산화물층(23)는, ITO/FT0; ITO/FTO-ITO; FTO/ITO; FTO/FTO; FTO/FTO-ITO; FTO-ITO/ITO; FTO-ITO/FTO; 또는 FTO-ITO/FTO-ITO; 일 수 있다. As an example of the present invention, the second oxide layer 23 may include an oxide having the same component as or different from that of the first oxide layer 21, and may include, for example, FTO; ITO; Or both, provided that the first oxide layer 21 / second oxide layer 23 is not composed of ITO / ITO. For example, at least one of the first oxide layer 21 and the second oxide layer 23 may include FTO, and at least one of the oxide layers including FTO may further include ITO. For example, the first oxide layer 21 / the second oxide layer 23 may include ITO / FT0; ITO / FTO-ITO; FTO / ITO; FTO / FTO; FTO / FTO-ITO; FTO-ITO / ITO; FTO-ITO / FTO; Or FTO-ITO / FTO-ITO; Can be.

예를 들어, 제2 산화물층(23)은, 제1 산화물층(21)과 동일하거나 또는 상이한 두께를 가질 수 있으며, 제2 산화물층(23)은, 10 nm 내지 100 nm; 바람직하게는 10 nm 내지 70 nm; 더 바람직하게는 10 nm 내지 50 nm의 두께를 가질 수 있다. For example, the second oxide layer 23 may have the same or different thickness as the first oxide layer 21, and the second oxide layer 23 may include 10 nm to 100 nm; Preferably 10 nm to 70 nm; More preferably, it may have a thickness of 10 nm to 50 nm.

본 발명의 일 예로, 본 발명에 의한 자외선 발광소자용 투명전극은, 360 nm 이하의 파장 영역에서 50 % 이상; 바람직하게는 85 % 이상의 광투과율을 나타낼 수 있다.In one embodiment of the present invention, the transparent electrode for ultraviolet light emitting device according to the present invention, 50% or more in the wavelength region of 360 nm or less; Preferably it can exhibit a light transmittance of 85% or more.

본 발명은, 본 발명에 의한 자외선 발광소자용 투명전극의 제조방법을 제공하는 것으로, 본 발명의 일 실시예에 따라, 상기 제조방법은, 단파장 영역에 대한 높은 투과율을 갖는 투명전극을 제공하고, 이러한 제조방법을 자외선 발광소자의 제조방법에 적용 시 발광소자의 제조단가를 낮출 수 있다.The present invention provides a method for manufacturing a transparent electrode for an ultraviolet light emitting device according to the present invention. According to an embodiment of the present invention, the manufacturing method provides a transparent electrode having a high transmittance for a short wavelength region, When the manufacturing method is applied to the manufacturing method of the ultraviolet light emitting device can reduce the manufacturing cost of the light emitting device.

본 발명의 일 실시예에 따라, 본 발명에 의한 제조방법은, 도 2를 참조하여 설명하며, 도 2는, 본 발명의 일 실시예에 따른, 본 발명의 자외선 발광소자용 투명전극의 제조방법에 대한 흐름도를 예시적으로 나타낸 것으로, 도 2에서 상기 제조방법은, 반도체층을 준비하는 단계(S1), 제1 산화물층을 형성하는 단계(S2), 금속층을 형성하는 단계(S3), 및 제2 산화물층을 형성하는 단계(S4)를 포함할 수 있고, 열처리하는 단계(S5)를 더 포함할 수 있다.According to an embodiment of the present invention, the manufacturing method according to the present invention will be described with reference to FIG. 2, and FIG. 2 is a method of manufacturing a transparent electrode for an ultraviolet light emitting device according to an embodiment of the present invention. For example, the manufacturing method of FIG. 2 includes preparing a semiconductor layer (S1), forming a first oxide layer (S2), forming a metal layer (S3), and The method may include forming a second oxide layer (S4), and may further include performing a heat treatment (S5).

본 발명의 일 예로, 반도체층을 준비하는 단계(S1)는, 자외선 발광소자의 광발생을 위한 반도체층(10)을 준비하는 단계이며, 자외선 발광소자에 적용가능한 반도체층이라면 제한 없이 적용될 수 있고, 예를 들어, 상기 반도체층은, 질화갈륨계 반도체 발광 다이오드를 포함하고, n-형 반도체층, 활성층 및 p-형 반도체층 등을 포함할 수 있으나, 하기의 발광소자에서 보다 구체적으로 설명한다.In one embodiment of the present invention, preparing the semiconductor layer (S1) is a step of preparing the semiconductor layer 10 for the light generation of the ultraviolet light emitting device, any semiconductor layer applicable to the ultraviolet light emitting device can be applied without limitation For example, the semiconductor layer may include a gallium nitride-based semiconductor light emitting diode, and may include an n-type semiconductor layer, an active layer, and a p-type semiconductor layer, but will be described in more detail with reference to the following light emitting devices. .

예를 들어, 반도체층을 준비하는 단계(S1)는, 본 발명의 기술 분야에서 적용되는 방법을 이용할 수 있으며, 예를 들어, CVD(chemical vapor deposition), PVD(physical vapor deposition), MOCVD(metal-organic chemical vapour deposition), MBE(Molecular Beam Epitaxy), HVPE(Hydride Vapour Phase Epitaxy) 등의 기상 성장 방법을 이용하여 반도체층을 형성할 수 있으나, 이에 제한하는 것은 아니다. For example, the preparing of the semiconductor layer (S1) may use a method applied in the technical field of the present invention, for example, chemical vapor deposition (CVD), physical vapor deposition (PVD), or MOCVD (metal). The semiconductor layer may be formed using a gas phase growth method such as organic chemical vapor deposition (MPE), molecular beam epitaxy (MBE), or hydraulic vapor phase epitaxy (HVPE), but is not limited thereto.

본 발명의 일 예로, 제1 산화물층을 형성하는 단계(S2)는, 반도체층(10) 상에 제1 산화물층(21)을 형성하는 단계이다.In an embodiment of the present invention, the forming of the first oxide layer (S2) is a step of forming the first oxide layer 21 on the semiconductor layer 10.

예를 들어, 제1 산화물층(21)은, 상기 투명전극에서 제시한 바와 같은 성분으로 구성된다.For example, the first oxide layer 21 is composed of the components as shown in the transparent electrode.

예를 들어, 제1 산화물층을 형성하는 단계(S2)는, 직류 마그네트론 스퍼터링, 라디오 주파수 마그네트론 스퍼터링 등의 스퍼터링법, 화학기상증착법(CVD), 열화학기상증착법(TCVD), 마이크로 웨이브 플라즈마 화학기상증착법(MPECVD), 용액 증착법 등을 이용할 수 있으며, 바람직하게는 스퍼터링법을 이용하여 제1 산화물층(21)을 성막할 수 있다. For example, the step (S2) of forming the first oxide layer may include sputtering, such as direct current magnetron sputtering, radio frequency magnetron sputtering, chemical vapor deposition (CVD), thermal chemical vapor deposition (TCVD), and microwave plasma chemical vapor deposition. (MPECVD), a solution vapor deposition method, or the like can be used. Preferably, the first oxide layer 21 can be formed by sputtering.

예를 들어, 상기 스퍼터링법에서 스퍼터링 타켓은 산화물 타켓 또는 금속타켓을 이용할 수 있고, 아르곤, 헬륨, 네온 가스 등과 같은 불활성 가스를 스퍼터 가스를 사용하고, 상기 스퍼터 가스에 산소, 이산화탄소 등과 같은 산화성 가스를 더 추가할 수 있으며, 산화성 가스는 스퍼터 가스의 10 % 이하로 사용할 수 있다. 예를 들어, 상기 스퍼터링법은, 아르곤 가스 유량 10 내지 20 sccm 및 산소 유량 1 내지 2 sccm으로 투입하고, 상온(25 ℃± 5℃) 이상의 온도에서 스퍼트 압력 1 내지 10 mTorr, 투입압력 90 W 내지 150 W에서 증착하고, 고온 성장시켜 산화물층을 형성할 수 있으며, 이러한 공정 조건은, 단지 예시적으로 기재되어 있을 뿐, 본 발명의 목적을 벗어나지 않는다면, 적절하게 선택하고 변경할 수 있다. For example, in the sputtering method, the sputtering target may use an oxide target or a metal target, use an inert gas such as argon, helium, neon gas, or the like as the sputter gas, and use an oxidizing gas such as oxygen or carbon dioxide as the sputter gas. Further oxidizing gas can be used with up to 10% of the sputter gas. For example, the sputtering method is introduced at an argon gas flow rate of 10 to 20 sccm and an oxygen flow rate of 1 to 2 sccm, at a temperature of 25 ° C. ± 5 ° C. or higher, and at a sputter pressure of 1 to 10 mTorr and an input pressure of 90 W to It can be deposited at 150 W and grown at high temperature to form an oxide layer, and these process conditions are only described by way of example and may be appropriately selected and modified without departing from the object of the present invention.

예를 들어, 제1 산화물층을 형성하는 단계(S2)에서 산화물이 다성분일 경우에, 각 성분을 코스퍼터링하여 제1 산화물층을 형성할 수 있으며, 예를 들어, 제1 산화물층이 FTO 및 ITO의 혼합층일 경우에, FTO 및 ITO는 동시에 코스퍼터링하여 형성될 수 있다.  For example, when the oxide is multi-component in the step of forming the first oxide layer (S2), each component may be coped to form the first oxide layer, for example, the first oxide layer may be FTO. And in the case of a mixed layer of ITO, FTO and ITO may be formed by co-sputtering at the same time.

본 발명의 일 예로, 금속층을 형성하는 단계(S3)는, 제1 산화물층(21) 상에 금속층(22)을 형성하는 단계이다. 금속층을 형성하는 단계(S3)는, 스퍼터링법 등을 이용하여 수행될 수 있고, 단계(S2)와 동일한 방법으로 성막될 수 있다.In one embodiment of the present invention, the forming of the metal layer (S3) is a step of forming the metal layer 22 on the first oxide layer 21. Step S3 of forming the metal layer may be performed using a sputtering method or the like, and may be formed in the same manner as step S2.

본 발명의 일 예로, 제2 산화물층을 형성하는 단계(S4)는, 금속층(22) 상에 제2 산화물층(23)을 형성하는 단계이다. 제2 산화물층을 형성하는 단계(S4)는, 직류 마그네트론 스퍼터링, 라디오 주파수 마그네트론 스퍼터링 등의 스퍼터링법, 화학기상증착법(CVD), 열화학기상증착법(TCVD), 또는 마이크로 웨이브 플라즈마 화학기상증착법(MPECVD), 용액 증착법 등을 이용할 수 있으며, 바람직하게는 스퍼터링법을 이용하여 제2 산화물층(23)을 성막할 수 있으며, 단계(S2)와 동일한 방법으로 수행될 수 있다.In one embodiment of the present invention, the forming of the second oxide layer (S4) is a step of forming the second oxide layer 23 on the metal layer 22. The step (S4) of forming the second oxide layer may include sputtering such as direct current magnetron sputtering, radio frequency magnetron sputtering, chemical vapor deposition (CVD), thermal chemical vapor deposition (TCVD), or microwave plasma chemical vapor deposition (MPECVD). , A solution deposition method, or the like may be used. Preferably, the second oxide layer 23 may be formed using a sputtering method, and may be performed in the same manner as in step S2.

본 발명의 일 예로, 투명전극의 제조방법은, 열처리하는 단계(S5)를 더 포함할 수 있다. 열처리하는 단계(S5)는, 제2 산화물층의 형성 이후에 제1 및 제2 산화물층의 산화를 진행시켜 산화물을 안정화시키고, 내부 결정계의 재결정화를 통해 전기적 특성을 확보할 뿐만 아니라, 성막의 그레인 사이의 간격을 증가시켜 투명 전극의 투명도를 증가시킬 수 있다. In one embodiment of the present invention, the method for manufacturing a transparent electrode may further include a step (S5) of heat treatment. In the heat treatment step (S5), after the formation of the second oxide layer, oxidation of the first and second oxide layers is performed to stabilize the oxides, and to secure electrical characteristics through recrystallization of the internal crystal system, Increasing the spacing between grains can increase the transparency of the transparent electrode.

예를 들어, 열처리하는 단계(S5)에서 열처리 온도는 100 ℃ 이상일 수 있고, 열처리에 따른 산화물층 입자의 불규칙한 형태 등에 따른 광학적 투과율의 저하를 방지하기 위해서, 바람직하게는 200 ℃ 내지 800 ℃ , 더 바람직하게는 300 ℃ 내지 700 ℃, 더 바람직하게는 500 ℃ 내지 700 ℃일 수 있다. 예를 들어, 열처리하는 단계(S5)는, 공기 분위기에서 1분 내지 1시간 동안 열처리될 수 있고, 바람직하게는 1분 내지 30분; 더 바람직하게는 1분 내지 15분일 수 있다. 상기 열처리 시간이 상기 범위 내에 포함되면, 산화가 원활하게 진행되고, 과도한 열처리에 따른 자외선 영역에 대한 투과도 저하를 방지할 수 있다. For example, the heat treatment temperature in the step (S5) of the heat treatment may be 100 ℃ or more, in order to prevent a decrease in the optical transmittance due to the irregular shape of the oxide layer particles due to the heat treatment, preferably 200 ℃ to 800 ℃, more Preferably from 300 ° C to 700 ° C, more preferably from 500 ° C to 700 ° C. For example, the heat treatment step (S5) may be heat treated for 1 minute to 1 hour in an air atmosphere, preferably 1 minute to 30 minutes; More preferably, it may be 1 to 15 minutes. When the heat treatment time is included in the above range, oxidation proceeds smoothly, and a decrease in transmittance of the ultraviolet region due to excessive heat treatment may be prevented.

본 발명은, 자외선 발광소자에 관한 것으로, 본 발명의 일 실시예에 따라, 상기 자외선 발광소자는, 본 발명에 의한 투명전극을 적용하여 기존의 ITO 전극에 따른 자외선 영역의 낮은 투과도를 개선하여 자외선 영역에 대한 고휘도를 나타낼 수 있다. 또한, 상기 자외선 발광소자는, 수직형 또는 수평형 epi-side up 구조로 제작이 가능하여 경제성이 향상될 수 있다. The present invention relates to an ultraviolet light emitting device, according to an embodiment of the present invention, the ultraviolet light emitting device, by applying a transparent electrode according to the present invention to improve the low transmittance of the ultraviolet region according to the conventional ITO electrode by ultraviolet light It can represent high brightness for the region. In addition, the ultraviolet light emitting device can be manufactured in a vertical or horizontal epi-side up structure can be improved economic efficiency.

본 발명의 일 실시예에 따라, 상기 발광소자는, 도 3을 참조하여 설명하며, 도 3은 본 발명의 일 실시예에 따른 본 발명에 의한 자외선 발광소자의 단면도를 예시적으로 나타낸 것이다. 도 3에서 발광소자는, 기판(110), 반도체층(130, 140, 150), 투명전극층(160) 및 전극(170)을 포함할 수 있고, 버퍼층(120)을 더 포함할 수 있다.According to an embodiment of the present invention, the light emitting device will be described with reference to FIG. 3, and FIG. 3 is a cross-sectional view of an ultraviolet light emitting device according to an embodiment of the present invention. In FIG. 3, the light emitting device may include a substrate 110, semiconductor layers 130, 140, and 150, a transparent electrode layer 160, and an electrode 170, and may further include a buffer layer 120.

본 발명의 일 예로, 기판(110)은, 본 발명의 기술 분야의 자외선 발광소자에 적용가능한 기판이라면 제한 없이 사용될 수 있고, 예를 들어, 사파이어, 다이아몬드, InP, AlGaN, LiAlO2, InN, GaP, Ge, InAs, AlAs, SiO2, Si, SiC, GaN, GaAs, 및 Al으로 이루어진 군에서 선택된 1종 이상을 포함할 수 있으나, 이에 제한하는 것은 아니다. As an example of the present invention, the substrate 110 may be used without limitation as long as it is a substrate applicable to an ultraviolet light emitting device of the technical field of the present invention. For example, sapphire, diamond, InP, AlGaN, LiAlO 2 , InN, GaP , Ge, InAs, AlAs, SiO 2 , Si, SiC, GaN, GaAs, and may include one or more selected from the group consisting of, but is not limited thereto.

본 발명의 일 예로, 반도체층(130, 140, 150)은, 기판(110) 상에 형성되며, 제1 반도체층(130), 활성층(140) 및 제2 반도체층(150)을 포함할 수 있다. For example, the semiconductor layers 130, 140, and 150 may be formed on the substrate 110 and include the first semiconductor layer 130, the active layer 140, and the second semiconductor layer 150. have.

예를 들어, 제1 반도체층(130)은, 와이드 밴드갭 반도체 화합물을 포함하고, 예를 들어, III-V계 반도체 화합물, II-VI계 반도체 화합물 또는 이 둘을 포함하는 N-형 반도체 화합물일 수 있다. 예를 들어, 상기 III-V계 반도체 화합물은, GaN, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, AlGaN, AlGaP, AlGaAs, AlGaSb, InGaN, GaInP, GaInAs, GaInSb, AlInN, AlInP, AlInAs, AlInSb, AlGaInN, AlGaInP, AlGaInAs 및 AlGaInSb으로 이루어진 군에서 선택된 1종 이상을 포함하고, 상기 II-VI계 반도체 화합물은, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, 및 CdTe으로 이루어진 군에서 선택된 1종 이상을 포함할 수 있다.For example, the first semiconductor layer 130 includes a wide bandgap semiconductor compound, for example, an III-V-based semiconductor compound, an II-VI-based semiconductor compound, or an N-type semiconductor compound including the two. Can be. For example, the III-V-based semiconductor compound is GaN, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, AlGaN, AlGaP, AlGaAs, AlGaSb, InGaN, GaInP, GaInAs, GaInSb , AlInN, AlInP, AlInAs, AlInSb, AlGaInN, AlGaInP, AlGaInAs and at least one selected from the group consisting of AlGaInSb, wherein the II-VI-based semiconductor compound, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, and It may include one or more selected from the group consisting of CdTe.

예를 들어, 활성층(140)은, 자외선 영역의 빛이 발생되는 영역이며, 단일 또는 다중 양자우물층을 포함할 수 있다. 활성층(140)은, III-V계 반도체 화합물을 포함하며, 예를 들어, GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, AlGaN, AlGaP, AlGaAs, AlGaSb, InGaN, GaInP, GaInAs, GaInSb, AlInN, AlInP, AlInAs, AlInSb, AlGaInN, AlGaInP, AlGaInAs 및 AlGaInSb으로 이루어진 군에서 선택된 1종 이상을 포함할 수 있으며, 상기 다중 양자구조는 AlN/AlGaN, AlN/GaN, AlN/InGaN, AlN/InN, AlN/AlGaInN, AlGaN/GaN, AlGaN/InGaN, AlGaN/AlGaInN, GaN/InGaN, GaN/InN, AlGaInN/InGaN, AlGaInN/InN, AlP/AlGaP, AlP/GaP, AlP/InGaP, AlP/InP, AlP/AlGaInP, AlGaP/GaP, 및 AlGaP/InGaP으로 이루어진 군에서 선택된 1종 이상을 포함할 수 있다. For example, the active layer 140 is a region where light in the ultraviolet region is generated, and may include a single or multiple quantum well layer. The active layer 140 includes a III-V-based semiconductor compound, for example, GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, AlGaN, AlGaP, AlGaAs, AlGaSb, InGaN, GaInP, GaInAs, GaInSb, AlInN, AlInP, AlInAs, AlInSb, AlGaInN, AlGaInP, AlGaInAs and AlGaInSb may include one or more selected from the group consisting of AlN / AlGaN, AlN / GaN, AlN / InGaN, AlN / InN, AlN / AlGaInN, AlGaN / GaN, AlGaN / InGaN, AlGaN / AlGaInN, GaN / InGaN, GaN / InN, AlGaInN / InGaN, AlGaInN / InN, AlP / AlGaP, AlP / GaP, It may include one or more selected from the group consisting of AlP / InGaP, AlP / InP, AlP / AlGaInP, AlGaP / GaP, and AlGaP / InGaP.

예를 들어, 제2 반도체층(150)은, III-V계 반도체 화합물, II-VI계 반도체 화합물 또는 이 둘을 포함하는 p-형 반도체 화합물일 수 있다. 예를 들어, 상기 III-V계 반도체 화합물은, GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, AlGaN, AlGaP, AlGaAs, AlGaSb, InGaN, GaInP, GaInAs, GaInSb, AlInN, AlInP, AlInAs, AlInSb, AlGaInN, AlGaInP, AlGaInAs 및 AlGaInSb으로 이루어진 군에서 선택된 1종 이상을 포함하고, 상기 II-VI계 반도체 화합물은 ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, 및 CdTe으로 이루어진 군에서 선택된 1종 이상을 포함할 수 있다.For example, the second semiconductor layer 150 may be a III-V-based semiconductor compound, a II-VI-based semiconductor compound, or a p-type semiconductor compound including the two. For example, the III-V-based semiconductor compound is GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, AlGaN, AlGaP, AlGaAs, AlGaSb, InGaN, GaInP, GaInAs , GaInSb, AlInN, AlInP, AlInAs, AlInSb, AlGaInN, AlGaInP, AlGaInAs and at least one selected from the group consisting of AlGaInSb, the II-VI-based semiconductor compound is ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, And it may include one or more selected from the group consisting of CdTe.

본 발명의 일 예로, 투명전극층(160)은, 반도체 화합물층(130, 140, 150)과 오믹컨택을 형성하는 것으로, 투명전극층(160)은, 활성층(140)에서 발광된 빛의 단파장 영역에 대한 고투과율을 나타내고, 가시광선 영역에 대한 높은 흡수율과 반사율을 제공하여, 고휘도의 자외선 발광소자를 제공할 수 있다. As an example of the present invention, the transparent electrode layer 160 forms ohmic contacts with the semiconductor compound layers 130, 140, and 150, and the transparent electrode layer 160 is formed in the short wavelength region of the light emitted from the active layer 140. By exhibiting high transmittance and providing high absorption and reflectance for the visible light region, it is possible to provide a high luminance ultraviolet light emitting device.

본 발명의 일 예로, 전극(170)은, 발광소자에 전류를 공급하여 전기구동을 가능하게 하는 것으로, 예를 들어, N형 전극(170a) 및 p형 전극(170b)을 포함할 수 있다. 예를 들어, n-형 금속 전극층(170a)은 Co, Ir, Ta, Cr, Mn, Mo, Tc, W, Re, Fe, Sc, Ti, Sn, Ge, Sb, Al, Pt, Ni, Au, ITO 및 ZnO 중 1종 또는 2종 이상의 혼합물로 이루어진, 단일층 또는 복수층으로 구성될 수 있다. 예를 들어, p-형 금속 전극층(170b)은 Co, Ir, Ta, Cr, Mn, Mo, Tc, W, Re, Fe, Sc, Ti, Sn, Ge, Sb, Al, Pt, Ni, Au, ITO 및 ZnO 중 1종 또는 2종 이상의 혼합물로 이루어진, 단일층 또는 복수층으로 구성될 수 있다. As an example of the present invention, the electrode 170 may supply electric current to the light emitting device to enable electric driving. For example, the electrode 170 may include an N-type electrode 170a and a p-type electrode 170b. For example, the n-type metal electrode layer 170a is formed of Co, Ir, Ta, Cr, Mn, Mo, Tc, W, Re, Fe, Sc, Ti, Sn, Ge, Sb, Al, Pt, Ni, Au It may consist of a single layer or a plurality of layers, consisting of one or a mixture of two or more of, ITO and ZnO. For example, the p-type metal electrode layer 170b includes Co, Ir, Ta, Cr, Mn, Mo, Tc, W, Re, Fe, Sc, Ti, Sn, Ge, Sb, Al, Pt, Ni, Au It may consist of a single layer or a plurality of layers, consisting of one or a mixture of two or more of, ITO and ZnO.

본 발명의 일 예로, 버퍼층(120)은, 제1 반도체층(130)의 성장을 용이하게 하기 위한 것으로, 도핑되지 않은 반도체 화합물을 포함하고, 예를 들어, III-V계 반도체 화합물, II-VI계 반도체 화합물 또는 이 둘을 포함할 수 있고, 상기 반도체 화합물은 상기 언급한 바와 같다. In one embodiment of the present invention, the buffer layer 120 is for facilitating the growth of the first semiconductor layer 130 and includes an undoped semiconductor compound, for example, a III-V-based semiconductor compound, II- VI-based semiconductor compound or both may be included, wherein the semiconductor compound is as mentioned above.

본 발명의 일 예로, 본 발명에 의한 자외선 발광소자는, 본 발명의 목적을 벗어나지 않는다면, 본 발명의 기술 분야에서 적용되는 자외선 발광소자의 구성을 더 포함할 수 있으며, 예를 들어, 투명전극층(160) 상에 전류확산층 등이 더 형성될 수 있으나, 이에 제한하는 것은 아니다. As an example of the present invention, the ultraviolet light emitting device according to the present invention may further include a configuration of the ultraviolet light emitting device applied in the technical field of the present invention, without departing from the object of the present invention, for example, a transparent electrode layer ( The current spreading layer may be further formed on the 160, but is not limited thereto.

하기와 같이, 본 발명의 바람직한 실시예를 참조하여 설명하지만, 해당 기술 분야의 숙련된 당업자는 하기의 특허 청구의 범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.As will be described below with reference to the preferred embodiments of the present invention, those skilled in the art various modifications of the present invention without departing from the spirit and scope of the invention described in the claims below. And can be changed.

실시예 1Example 1

사파이어 기판 상에 n-GnN/MQW이 형성된 반도체층을 제조하고, 상기 반도체층 상에 스퍼터링 가스(Ar), 온도(500 ℃), 및 압력(3 mTorr) 하에서 FTO-ITO(70 nm, FTO:ITO=1:1)/Ag(14 nm)/FTO-ITO(70 nm) 박막의 투명전극이 형성된 UV-LED를 제조하였다. 투명전극의 표면에 대한 SEM 이미지를 측정하여 도 4a에 나타내고, UV-spectrometer 장치를 이용하여 광투과도를 측정하여 도 5에 나타내었다. A semiconductor layer having n-GnN / MQW formed on a sapphire substrate was prepared, and FTO-ITO (70 nm, FTO :) was formed on the semiconductor layer under sputtering gas (Ar), temperature (500 ° C.), and pressure (3 mTorr). A UV-LED having a transparent electrode of ITO = 1: 1) / Ag (14 nm) / FTO-ITO (70 nm) thin film was prepared. The SEM image of the surface of the transparent electrode was measured and shown in FIG. 4A, and the light transmittance was measured and shown in FIG. 5 using a UV-spectrometer apparatus.

실시예 2Example 2

FTO-ITO(50 nm, FTO:ITO=1:1)/Ag(14 nm)/FTO-ITO(50 nm, FTO:ITO=1:1) 박막의 투명전극을 형성한 것 외에는 실시예 1과 동일한 방법으로 UV-LED를 제조하였다. 투명전극의 표면에 대한 SEM 이미지를 측정하여 도 4b에 나타내고, UV-spectrometer 장치를 이용하여 광투과도를 측정하여 도 5에 나타내었다. Example 1 except that a transparent electrode of FTO-ITO (50 nm, FTO: ITO = 1: 1) / Ag (14 nm) / FTO-ITO (50 nm, FTO: ITO = 1: 1) thin film was formed. UV-LEDs were manufactured in the same manner. The SEM image of the surface of the transparent electrode was measured and shown in FIG. 4B, and the light transmittance was measured and shown in FIG. 5 using a UV-spectrometer apparatus.

실시예 3Example 3

FTO-ITO(50 nm, FTO:ITO=1:1)/Ag(14 nm)/FTO-ITO(50 nm, FTO:ITO=1:1) 박막의 투명전극을 실시예 2와 동일한 방법으로 UV-LED를 제조하였다. 상기 UV-LED 는 500 ℃ 온도에서 1분 동안 열처리하였다. 열처리 후의 투명전극의 표면에 대한 SEM 이미지를 측정하여 도 4c에 나타내고, UV-spectrometer 장치를 이용하여 광투과도를 측정하여 도 5 및 도 6에 나타내었다. The transparent electrode of the thin film of FTO-ITO (50 nm, FTO: ITO = 1: 1) / Ag (14 nm) / FTO-ITO (50 nm, FTO: ITO = 1: 1) was UV-treated in the same manner as in Example 2. -LED was manufactured. The UV-LED was heat treated at 500 ° C. for 1 minute. The SEM image of the surface of the transparent electrode after the heat treatment was measured and shown in FIG. 4C, and the light transmittance was measured in the UV-spectrometer apparatus and shown in FIGS. 5 and 6.

실시예 4Example 4

FTO(50 nm)/Ag(14 nm)/FTO(50 nm) 박막의 투명전극을 실시예 1과 동일한 방법으로 UV-LED를 제조하였다. 상기 UV-LED 는 500 ℃ 온도에서 1분 동안 열처리하였다. UV-spectrometer 장치를 이용하여 광투과도를 측정하여 도 6에 나타내었다. UV-LED was prepared in the same manner as in Example 1 using a transparent electrode of FTO (50 nm) / Ag (14 nm) / FTO (50 nm) thin film. The UV-LED was heat treated at 500 ° C. for 1 minute. The light transmittance was measured using a UV-spectrometer device and is shown in FIG. 6.

비교예 1Comparative Example 1

ITO(50 nm)/Ag(14 nm)/ITO(50 nm) 박막의 투명전극을 형성한 것 외에는 실시예 3과 동일한 방법으로 UV-LED를 제조하고 열처리하였다. UV-spectrometer 장치를 이용하여 광투과도를 측정하여 도 6에 나타내었다. A UV-LED was manufactured and heat-treated in the same manner as in Example 3 except that a transparent electrode of an ITO (50 nm) / Ag (14 nm) / ITO (50 nm) thin film was formed. The light transmittance was measured using a UV-spectrometer device and is shown in FIG. 6.

도 4 내지 도 6을 살펴보면, 도 4a, 도 4b, 도 4c 및 도 5에서 산화물층의 두께가 얇은 실시예 2의 투명전극은, 산화물층의 입자 그레인이 증가되고, 자외선 영역에 대한 투과도가 실시예 1에 비하여 증가된 것을 확인할 수 있다. 또한, 열처리된 투명전극(실시예 3)이, 월등하게 증가된 자외선 투과도를 나타내고 있으며, 이는 열처리 시 산화물층의 재결정화에 따른 안정화 및 산화물층의 그레인 증가에 따라 자외선 영역에 대한 투과도를 개선시킨 것으로 예측할 수 있다.4 to 6, in the transparent electrode of Example 2 having a thin oxide layer in FIGS. 4A, 4B, 4C, and 5, particle grains of the oxide layer are increased and transmittance in the ultraviolet region is performed. It can be seen that compared with Example 1. In addition, the heat-treated transparent electrode (Example 3) exhibited a significantly increased ultraviolet transmittance, which was improved by stabilization due to recrystallization of the oxide layer during heat treatment and improved grain permeability due to an increase in grain size of the oxide layer. Can be predicted.

또한, 도 6을 살펴보면, 본 발명에 의한 FTO를 포함하는, 실시예 3 및 실시예 4는, 비교예 1의 ITO-OMO(oxide/metal/oxide) 구조의 투명전극에 비하여 360 nm 이하의 자외선 영역에서 월등하게 증가된 투과도를 제공하는 것을 확인할 수 있다. 이는, 본 발명에 의한 FTO를 포함하는 산화물층을 투명전극에 적용할 경우에, 기존에 사용된 ITO 기반 투명전극에 비하여 자외선 투과도를 개선시킬 수 있음을 보여주는 것이다. In addition, referring to Figure 6, Example 3 and Example 4, including the FTO according to the present invention, compared to the transparent electrode of the ITO-OMO (oxide / metal / oxide) structure of Comparative Example 1 UV of 360 nm or less It can be seen that it provides a significantly increased transmittance in the region. This shows that, when the oxide layer including the FTO according to the present invention is applied to a transparent electrode, the UV transmittance can be improved as compared with the conventional ITO-based transparent electrode.

본 발명에 의한 FTO를 포함하는 산화물층을 적용한 자외선 발광소자용 투명전극은, 단파장 자외선 영역에 대한 높은 투과도를 제공하고, 자외선 발광소자의 효율을 향상시킬 수 있다. 또한, 본 발명에 의한 투명전극을 자외선 발광소자에 적용할 경우에, 수평형 또는 수직형 자외선 발광소자의 제조가 가능하여 기존의 플립칩 구조로 제조되는 자외선 발광소자에 비하여 제조단가를 낮출 수 있다. The transparent electrode for an ultraviolet light emitting device to which the oxide layer including the FTO according to the present invention is applied can provide a high transmittance to a short wavelength ultraviolet region and improve the efficiency of the ultraviolet light emitting device. In addition, when the transparent electrode according to the present invention is applied to an ultraviolet light emitting device, it is possible to manufacture a horizontal or vertical ultraviolet light emitting device can lower the manufacturing cost compared to the ultraviolet light emitting device manufactured with a conventional flip chip structure. .

Claims (20)

제1 산화물층; 상기 제1 산화물층 상에 형성된 금속층; 및 상기 금속층 상에 형성된 제2 산화물층; 을 포함하고, A first oxide layer; A metal layer formed on the first oxide layer; And a second oxide layer formed on the metal layer. Including, 상기 제1 산화물층 및 제2 산화물층 중 적어도 어느 하나는, FTO(fluorine doped tin oxide)를 포함하는 것인, At least one of the first oxide layer and the second oxide layer, which includes fluorine doped tin oxide (FTO), 자외선 발광소자용 투명전극.Transparent electrode for ultraviolet light emitting device. 제1항에 있어서,The method of claim 1, 상기 FTO를 포함하는 상기 제1 산화물 및 제2 산화물층 중 적어도 어느 하나는 ITO를 더 포함하는 FTO-ITO 혼합층인 것인, 자외선 발광소자용 투명전극. At least one of the first oxide and the second oxide layer containing the FTO is an FTO-ITO mixed layer further comprising ITO, transparent electrode for ultraviolet light emitting device. 제2항에 있어서,The method of claim 2, 상기 혼합층 중 FTO:ITO 몰비는 1:1에서 1:5까지 변화하는 것인, 자외선 발광소자용 투명전극. FTO: ITO molar ratio of the mixed layer is from 1: 1 to 1: 5, the transparent electrode for ultraviolet light emitting device. 제1항에 있어서,The method of claim 1, 상기 제1 산화물층/제2 산화물층은, ITO/FT0; ITO/FTO-ITO; FTO/ITO; FTO/FTO; FTO/FTO-ITO; FTO-ITO/ITO; FTO-ITO/FTO; 또는 FTO-ITO/FTO-ITO; 인 것인, 자외선 발광소자용 투명전극. The first oxide layer / second oxide layer is ITO / FT0; ITO / FTO-ITO; FTO / ITO; FTO / FTO; FTO / FTO-ITO; FTO-ITO / ITO; FTO-ITO / FTO; Or FTO-ITO / FTO-ITO; That is, a transparent electrode for ultraviolet light emitting elements. 제1항에 있어서,The method of claim 1, 상기 제1 산화물층 및 제2 산화물층은 각각, 10 nm에서 100 nm까지 두께를 갖는 것인, 자외선 발광소자용 투명전극. The first oxide layer and the second oxide layer, respectively, having a thickness from 10 nm to 100 nm, a transparent electrode for ultraviolet light emitting device. 제1항에 있어서,The method of claim 1, 상기 금속층은, Ag, Au, Pd, Al, Pt, Cu, Zn, Cd, In, Si, Zr, Mo, Ni, Cr, Mg, Mn, Co 및 Sn으로 이루어진 군에서 선택된 1종 이상을 포함하는 것인, 자외선 발광소자용 투명전극.The metal layer includes at least one selected from the group consisting of Ag, Au, Pd, Al, Pt, Cu, Zn, Cd, In, Si, Zr, Mo, Ni, Cr, Mg, Mn, Co, and Sn. Will, transparent electrode for ultraviolet light emitting element. 제1항에 있어서,The method of claim 1, 상기 금속층은, 1 nm 내지 50 nm 두께를 갖는 것인, 자외선 발광소자용 투명전극.The metal layer has a thickness of 1 nm to 50 nm, a transparent electrode for ultraviolet light emitting device. 제1항에 있어서,The method of claim 1, 상기 투명전극은 360 nm 이하의 파장에서 광투과율이 85 % 이상인 것인, 자외선 발광소자용 투명전극.The transparent electrode has a light transmittance of 85% or more at a wavelength of 360 nm or less, a transparent electrode for ultraviolet light emitting device. 제1항의 투명전극을 포함하는, 자외선 발광소자.An ultraviolet light emitting device comprising the transparent electrode of claim 1. 제9항에 있어서,The method of claim 9, 반도체층;A semiconductor layer; 상기 반도체층의 적어도 일면에 형성된 투명전극층; 및 A transparent electrode layer formed on at least one surface of the semiconductor layer; And 상기 투명전극층의 적어도 일부분에 형성된 전극; 을 포함하는 것인, 발광 소자.An electrode formed on at least a portion of the transparent electrode layer; To include, the light emitting device. 제10항에 있어서,The method of claim 10, 상기 반도체층 및 상기 투명전극층 사이에 버퍼층을 더 포함하는 것인, 발공 소자.The pore device further comprises a buffer layer between the semiconductor layer and the transparent electrode layer. 제11항에 있어서,The method of claim 11, 상기 버퍼층은, III-V계 반도체 화합물, II-VI계 반도체 화합물 또는 이 둘을 포함하는 것인, 발광 소자.The buffer layer is a light emitting device comprising a III-V-based semiconductor compound, a II-VI-based semiconductor compound or both. 제10항에 있어서,The method of claim 10, 상기 반도체층은, 제1 반도체층; 제2 반도체층; 및 상기 제1 반도체층 및 상기 제2 반도체층 사이에 활성층을 포함하는 것인, 발광 소자.The semiconductor layer includes a first semiconductor layer; A second semiconductor layer; And an active layer between the first semiconductor layer and the second semiconductor layer. 제13항에 있어서, The method of claim 13, 상기 활성층은, 양자구조를 포함하는 것인, 발광 소자. The active layer is a light emitting device comprising a quantum structure. 반도체층 상에 제1 산화물층을 형성하는 단계;Forming a first oxide layer on the semiconductor layer; 상기 제1 산화물층 상에 금속층을 형성하는 단계; 및Forming a metal layer on the first oxide layer; And 상기 금속층 상에 제2 산화물층을 형성하는 단계;Forming a second oxide layer on the metal layer; 를 포함하고,Including, 상기 제1 산화물층 및 제2 산화물층 중 적어도 어느 하나는, FTO를 포함하는 것인, 자외선 발광소자용 투명전극의 제조방법.At least one of the first oxide layer and the second oxide layer, the manufacturing method of a transparent electrode for ultraviolet light emitting element, which comprises FTO. 제15항에 있어서,The method of claim 15, 상기 FTO를 포함하는 상기 제1 산화물 및 제2 산화물층 중 적어도 어느 하나는 ITO를 더 포함하는 FTO-ITO 혼합층하는 것인, 자외선 발광소자용 투명전극의 제조방법.At least one of the first oxide and the second oxide layer including the FTO is a FTO-ITO mixed layer further comprising ITO, the manufacturing method of the transparent electrode for ultraviolet light emitting device. 제16항에 있어서,The method of claim 16, 상기 혼합층을 형성하는 단계는, 코스퍼터링으로 수행하는 것인, 자외선 발광소자용 투명전극의 제조방법.Forming the mixed layer is to be carried out by the coping, manufacturing method of the transparent electrode for ultraviolet light emitting device. 제15항에 있어서,The method of claim 15, 상기 제2 산화물층을 형성하는 단계 이후에 열처리하는 단계를 더 포함하는 것인, 자외선 발광소자용 투명전극의 제조방법.The method of manufacturing a transparent electrode for an ultraviolet light emitting device further comprising the step of heat treatment after the step of forming the second oxide layer. 제18항에 있어서,The method of claim 18, 상기 열처리하는 단계는, 100 ℃ 이상의 온도에서 열처리하는 것인, 자외선 발광소자용 투명전극의 제조방법.The heat treatment step, the heat treatment at a temperature of 100 ℃ or more, the manufacturing method of the transparent electrode for ultraviolet light emitting device. 제18항에 있어서,The method of claim 18, 상기 열처리하는 단계는, 1분 내지 1시간동안 열처리하는 것인, 자외선 발광소자용 투명전극의 제조방법.The heat treatment is a heat treatment for 1 minute to 1 hour, a method for manufacturing a transparent electrode for ultraviolet light emitting device.
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