CN107706278B - Preparation method and application of transparent electrode of ultraviolet light-emitting diode - Google Patents
Preparation method and application of transparent electrode of ultraviolet light-emitting diode Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052738 indium Inorganic materials 0.000 claims abstract description 24
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 24
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
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- 238000000034 method Methods 0.000 claims abstract description 15
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- 150000004767 nitrides Chemical class 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 229910003437 indium oxide Inorganic materials 0.000 claims abstract description 6
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 3
- 238000007781 pre-processing Methods 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims description 6
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical group C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 claims description 6
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical compound C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 230000009643 growth defect Effects 0.000 claims description 2
- RWWNQEOPUOCKGR-UHFFFAOYSA-N tetraethyltin Chemical compound CC[Sn](CC)(CC)CC RWWNQEOPUOCKGR-UHFFFAOYSA-N 0.000 claims description 2
- CRHIAMBJMSSNNM-UHFFFAOYSA-N tetraphenylstannane Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CRHIAMBJMSSNNM-UHFFFAOYSA-N 0.000 claims description 2
- 229910001868 water Inorganic materials 0.000 claims description 2
- -1 dimethylamino tin Chemical compound 0.000 claims 1
- 239000001272 nitrous oxide Substances 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 30
- 238000002834 transmittance Methods 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- WHXTVQNIFGXMSB-UHFFFAOYSA-N n-methyl-n-[tris(dimethylamino)stannyl]methanamine Chemical compound CN(C)[Sn](N(C)C)(N(C)C)N(C)C WHXTVQNIFGXMSB-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- 239000002585 base Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 description 1
- GRPQBOKWXNIQMF-UHFFFAOYSA-N indium(3+) oxygen(2-) tin(4+) Chemical compound [Sn+4].[O-2].[In+3] GRPQBOKWXNIQMF-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 235000013842 nitrous oxide Nutrition 0.000 description 1
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- 150000007524 organic acids Chemical class 0.000 description 1
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- 239000000243 solution Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
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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
- H01L33/36—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 electrodes
- H01L33/40—Materials therefor
- H01L33/42—Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0016—Processes relating to electrodes
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- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
- Electrodes Of Semiconductors (AREA)
- Led Devices (AREA)
Abstract
The invention discloses a Metal Organic Chemical Vapor Deposition (MOCVD) preparation method for a transparent electrode of an ultraviolet LED. The method is characterized in that a functional adjusting layer is grown in situ before tin-doped indium oxide (ITO) is deposited as a main body layer. The invention also discloses how to grow the function regulating layer and the main body layer in situ, and the function regulating layer and the main body layer are sequentially grown on the surface of the ultraviolet LED epitaxial wafer as a growth substrate material, and the method comprises the following steps: preprocessing a growth substrate; introducing one or a mixture of an indium source and a tin source into the surface of the nitride-based ultraviolet LED epitaxial wafer to form a function adjusting layer; and an indium source, a tin source and an oxygen source are introduced into the function adjusting layer to grow an ITO film to form a main body layer. The ITO transparent conductive film provided by the invention has low forward working voltage, extremely high reliability and high-efficiency light extraction efficiency when being applied to a nitride-based ultraviolet LED device, and can greatly promote the application of an ultraviolet light electric device.
Description
Technical Field
The invention relates to the technical field of semiconductor materials and semiconductor photoelectric devices, in particular to a preparation method and application of a transparent electrode of an ultraviolet light-emitting diode.
Background
For the transparent electrode film of the nitride-based Light Emitting Diode (LED), materials such as nickel-gold alloy (Ni/Au), zinc oxide-based transparent electrode, and Indium Tin Oxide (ITO) are mainly used.
The transparent conductive film has high transmittance in a visible light range (400nm-760nm) and low resistivity, is widely applied to the fields of flat panel display, solar cells, light-emitting devices, photoelectric detectors and the like, and has wide application prospect. In recent years, photoelectric devices in the ultraviolet band have been developed rapidly, and when used as transparent electrodes of ultraviolet LEDs, transparent conductive films are required to have three characteristics: high transmittance of ultraviolet band, high conductivity of the film, and low specific contact resistance between the film and the ultraviolet LED. Accordingly, the current preparation of transparent electrode materials suitable for uv LEDs is mainly faced with two difficulties: firstly, how to prepare a conductive film with higher transmittance in an ultraviolet band; on the other hand, how to reduce the specific contact resistance of the transparent conductive material and the LED will also greatly affect the performance of the device due to the poor conductivity characteristics of the p-type layer on the top layer of the ultraviolet LED.
At present, the oxide transparent electrode mainly includes a ZnO-based transparent electrode, an indium oxide-based transparent electrode, and the like. The indium oxide tin-doped (ITO) has the advantages of high light transmittance, good conductivity, good thermal stability, strong substrate adhesion and the like, and is the transparent conductive film which is most widely used and has the mature process at present. Meanwhile, the ITO thin film growth methods mainly include magnetron sputtering, Molecular Beam Epitaxy (MBE), laser pulse deposition (PLD), and the like, but the transmittance of the transparent conductive thin film prepared by these methods is generally lower than 80% in the ultraviolet band, especially in the ultraviolet band around 365 nm. The ITO film grown by MOCVD not only has the conductivity (the resistivity is lower than 4 x 10) similar to that of other growth methods-4Ω · cm) and a transmittance in the 365nm band of more than 90%, and is therefore suitable as a transparent electrode for an ultraviolet LED. It is therefore critical to solve the problem of ITO contact with the LED.
The transparent electrode prepared by the conventional method generally uses a single growth condition, and the prepared film has higher conductivity and transmittance; however, the transparent conductive film prepared under such conditions does not necessarily achieve a low specific contact resistance with the LED. It is reported in the literature that contact can be generally improved by interfacial treatment or insertion of a contact layer, as early as 1999, j.s.jang et al treated GaN surfaces by using a two-step process, boiling BOE and boiling (NH), respectively4)2SxEach treatment was performed for ten minutes to remove the surface oxide and reduce the schottky barrier by using a chemical method to achieve a reduction in contact resistance with the p-GaN. (document: J. -S.Jang., S. -J.park, and T. -Y.Seong, Journal of vacuum science and Technology B, Microelectron., vol.17, No.6, pp.2667-2670, Nov.1999.). The team of Jang and Liu et al inserted a strained layer on the blue LED, such as: p-InGaN-GaN, p-GaN/i-InGaN superlattice structures and n +/p + -GaN, n + -InGaN/GaN are used as tunneling layers, thereby achieving the effects of improving contact and reducing working voltage (J.S. Jang, Applied Physics Letters, vol).93,no.8,pp.081118-1–081118-3,Aug.2008.；Y.J.Liu,C.H.Yen,L.Y.Chen,T.H.Tsai,T.Y.Tsai,and W.C.Liu,IEEEElectron Device Lett,vol.30,no.11,pp.1149–1151,Nov.2009.)。
Disclosure of Invention
The invention is made aiming at the problems, the film is prepared by using the MOCVD method, different growth conditions can be effectively regulated and controlled, and the film with a multilayer structure can be flexibly prepared. Therefore, the MOCVD is utilized to prepare the transparent electrode for the ultraviolet LED, and the main body layer of the transparent electrode plays the role of the main transparent electrode; different growth conditions are adopted before the main body layer is grown, a function adjusting layer capable of improving the contact characteristic with the LED is grown, the specific contact resistance can be effectively reduced, the working efficiency of the LED is improved, meanwhile, the indium oxide tin (ITO) doped transparent conductive film is provided, and the problem of low transmittance of the oxide transparent conductive film applied to an ultraviolet Light Emitting Diode (LED) device is effectively solved.
The specific technical scheme includes that the indium oxide tin-doped (ITO) transparent conductive film is characterized in that the ITO transparent electrode comprises a function regulating layer and a main body layer which are sequentially epitaxially grown on an ultraviolet LED.
Preferably, the substrate material is a nitride-based LED epitaxial wafer, in particular an ultraviolet LED epitaxial wafer.
Preferably, the function adjusting layer uses one or both of an organic metal indium source and a tin source as a growth source, and the growth time of the function adjusting layer is 6 to 60 seconds.
Preferably, the main body layer is an ITO film grown on the function adjusting layer by sharing an indium source, a tin source and an oxygen source, and the thickness of the main body layer is 40nm-500 nm.
The preparation method of the transparent electrode of the ultraviolet light-emitting diode is characterized by comprising the following steps: before depositing the main body layer of the transparent electrode, a functional regulating layer which can improve the transparent electrode is grown in situ, the specific steps are as follows,
step one, preprocessing a growth substrate material, namely, in an epitaxial device, carrying out acid-base chemical cleaning and high-temperature treatment of more than 500 ℃ on the surface of an epitaxial wafer serving as the growth substrate material, and effectively removing dirty points of the surface of the epitaxial wafer, which can cause material growth defects;
step two, growing a function regulating layer, namely introducing a regulating layer growth source on the surface of the pretreated epitaxial wafer in an epitaxial device under a protective atmosphere (such as argon or nitrogen) to grow a function regulating layer, wherein the growth temperature of the function regulating layer is 400-600 ℃, and the pressure of a reaction furnace in the device is 6-80 torr;
growing a main body layer, introducing a main body layer growth source on the function regulating layer under a protective atmosphere (such as argon or nitrogen), growing an indium oxide tin-doped transparent conductive film to form the main body layer, wherein the growth temperature of the main body layer is 400-600 ℃, and the pressure of a reaction furnace in the equipment is 6-80 torr;
the function adjusting layer and the main body layer are both grown by using a metal organic chemical vapor deposition method.
Further, in the step one, the pretreatment specifically comprises the steps of firstly, respectively carrying out ultrasonic treatment on the epitaxial wafer for 5min by using acetone and IPA (isopropyl alcohol solution); and then cleaning with deionized water, drying with nitrogen, soaking with sulfuric acid and hydrogen peroxide in a ratio of 2:1 for 15min, cleaning with deionized water, drying with nitrogen, placing in a growth cavity, performing high-temperature treatment at 530 ℃ on the ITO growth furnace, and keeping the temperature constant for 10 min.
Further, in the second step, the surface of the epitaxial wafer refers to the p-GaN surface of the nitride-based LED.
Furthermore, in-situ growth is to improve the contact between the growing ITO and the surface of the LED, before the ITO is grown by MOCVD, only an MO source is introduced to grow a layer of pre-laying layer under the condition of reaching the same temperature and cavity for growing the ITO film, and the growing process of the pre-laying layer is called as in-situ growth. (the MO source specifically refers to TDMASn, TMIn source or a mixture of both sources)
Preferably, the growth substrate material is a nitride-based ultraviolet LED epitaxial wafer.
Preferably, the function adjusting layer uses an indium source or a tin source as an adjusting layer growth source.
Preferably, the function control layer uses a mixed source of an indium source and a tin source as a common growth source of the function control layer.
Preferably, the bulk layer uses a source of indium, a source of tin and a source of oxygen in common as a source for bulk layer growth.
Preferably, the indium source is trimethylindium (TMIn);
the tin source can be an organotin source such as tetrakis (dimethylamino) tin, tetraethyltin, dimethyltin, tetraphenyltin, and the like.
Preferably, the oxygen source can be oxygen gas, laughing gas, water, ozone and the like.
Preferably, the molar flow ratio of the indium source to the tin source is from 4:1 to 100:1, wherein the flow rate of the indium source is from 8E-6 to 8E-5 moles/minute and the flow rate of the tin source is from 8E-7 to 1.5E-5 moles/minute.
Preferably, the growth time of the function-regulating layer is 6 to 60 seconds.
Preferably, the molar flow ratio of the indium source to the tin source is from 4:1 to 100:1, the molar flow ratio of the indium source to the oxygen source is from 1:550 to 1:5500, and the oxygen flow rate is from 8E-3 to 2.5E-1 mol/min.
Preferably, the bulk layer is grown to a thickness of 40-500 nm.
The invention also provides an application of the ultraviolet light-emitting diode transparent electrode, which is characterized in that: the transparent electrode can be used as a transparent electrode layer of a nitride ultraviolet LED with the luminous wavelength of 300-420 nm.
Advantageous effects
By adopting the technical scheme, the invention at least has the following advantages: by adopting the ITO transparent electrode prepared by the invention, the contact layer can effectively reduce the specific contact resistance of an ITO material and a nitride-based LED epitaxial wafer p-type material, the main body layer has lower resistivity and higher transmittance of an ultraviolet wave band, the effective transverse expansion of the injection current can be ensured, the surface of the epitaxial wafer can be coarsened by the function adjusting layer, the optical extraction efficiency can be increased, and the light emitting efficiency can be effectively improved; therefore, the ITO transparent conductive film prepared by the preparation method of the ITO transparent electrode has low forward working voltage, high reliability and high-efficiency light extraction efficiency when being applied to a nitride-based ultraviolet LED device, and can greatly promote the application of an ultraviolet photoelectric device.
Drawings
Fig. 1 is a schematic diagram of a full structure of a functional regulation layer and a transparent electrode main body layer grown in situ on the basis of an ultraviolet LED epitaxial wafer according to the technical scheme of the present invention.
Fig. 2 is a scanning electron microscope image of the ITO film of the main layer of the present invention In which an In source is pre-laid for 6 seconds before the ITO film is grown as a function adjusting layer In embodiment 1, and compared with the ITO film of the main layer which is not pre-laid, the surface is significantly roughened, thereby improving the light extraction efficiency.
FIG. 3 is a graph of transmittance at 200-800nm wavelength band after pre-laying Sn source for 6 seconds as a function adjusting layer before growing ITO film of the main layer in the embodiment 2 of the present invention, wherein the thickness of the film is 80nm, and the transmittance at 365nm wavelength band is 95.9%.
Detailed Description
The following further describes embodiments of the present invention with reference to the accompanying drawings:
example 1
By utilizing the existing MOCVD equipment, organic metal trimethyl indium is used as an indium source, organic metal tetra (dimethylamino) tin source, oxygen with the purity of 99.9999 percent is used as an oxygen source, argon is used as carrier gas and growth protective atmosphere, a function adjusting layer with the organic metal In source paved In advance is grown on an epitaxial wafer ultraviolet 365nm LED, and then an ITO film is deposited to be used as a main body layer.
The preparation method of the function adjusting layer and the main body layer comprises the following steps:
1. pretreatment before growth of a substrate: a365 nm ultraviolet LED epitaxial wafer is used as a substrate material, and the surface of the substrate material is cleaned by organic and inorganic acid-base to prevent air from contacting and then is placed into an MOCVD reaction cavity as soon as possible.
2. And (3) growth of a functional regulation layer: the growth temperature is controlled at 530 ℃, the pressure of the reaction cavity is controlled at 9Torr, only the indium source is introduced, and the processing time is 6 seconds.
3. And (3) growing a main body layer: the growth temperature is continuously controlled at 530 ℃, the pressure of the reaction cavity is continuously controlled at 9Torr, and at the moment, an indium source, a tin source and an oxygen source are simultaneously introduced, and an 80nm ITO film is grown as a main body layer on the basis of the function adjusting layer.
4. And (3) directly growing the ITO transparent electrode according to the same method of the steps except the step 2).
As shown in fig. 2, a comparison between the sem images of the growth function adjusting layer and the ITO transparent electrode and the sem image of the non-growth function adjusting layer in this embodiment can obtain: the surface roughness of the LED with the function adjusting layer is increased, and the light emitting efficiency of the LED forward-mounted chip can be improved.
Example 2
By utilizing the existing MOCVD equipment, organic metal trimethyl indium is used as an indium source, organic metal tetra (dimethylamino) tin source, oxygen with the purity of 99.9999 percent is used as an oxygen source, argon is used as carrier gas and growth protective atmosphere, a function adjusting layer of pre-paved organic metal Sn is grown on an epitaxial wafer ultraviolet 365nm LED, and then an ITO film is deposited to be used as a main body layer.
The preparation method of the function adjusting and main body layer comprises the following steps:
1. pretreatment before growth of a substrate: a365 nm ultraviolet LED epitaxial wafer is used as a substrate material, and the surface of the substrate material is cleaned by organic and inorganic acid and alkali to prevent air from contacting and is placed into an MOCVD reaction cavity as soon as possible.
2. And (3) growth of a functional regulation layer: the growth temperature is controlled at 530 ℃, the pressure of the reaction cavity is controlled at 9Torr, only the tin source is introduced, and the processing time is 6 seconds.
3. And (3) growing a main body layer: the growth temperature is continuously controlled at 530 ℃, the pressure of the reaction cavity is continuously controlled at 9Torr, and at the moment, an indium source, a tin source and an oxygen source are simultaneously introduced, and an 80nm ITO film is grown as a main body layer on the basis of the function adjusting layer.
Referring to FIG. 3, a transmittance graph at 200-800nm wavelength band is obtained after 6 seconds of Sn source is pre-laid before growing ITO film, wherein the thickness of the film is 80nm, and the transmittance at 365nm wavelength band is as high as 95.9%.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (6)
1. A preparation method of a transparent electrode of an ultraviolet light-emitting diode is characterized by comprising the following steps: before depositing the main body layer of the transparent electrode, a functional regulating layer which can improve the transparent electrode is grown in situ, the specific steps are as follows,
step one, preprocessing a growth substrate material, namely, in an epitaxial device, carrying out acid-base chemical cleaning and high-temperature treatment at the temperature of more than 500 ℃ on the surface of an epitaxial wafer serving as the growth substrate material, and effectively removing dirty points of the surface of the epitaxial wafer, which can cause material growth defects;
growing a function adjusting layer, namely introducing an indium source or a tin source or a mixed metal source of the indium source and the tin source into the surface of the pretreated epitaxial wafer in a protective atmosphere in epitaxial equipment to grow a function adjusting layer, wherein the growth temperature of the function adjusting layer is 400-600 ℃, and the pressure of a reaction furnace in the equipment is 6-80 torr;
growing a main body layer, introducing an organic metal source containing tin and indium and an oxygen source into the function regulating layer under a protective atmosphere, and growing an indium oxide tin-doped transparent conductive film to form the main body layer, wherein the growth temperature of the main body layer is 400-600 ℃, and the pressure of a reaction furnace in the equipment is 6-80 torr;
the function adjusting layer and the main body layer are grown by using a metal organic chemical vapor deposition method;
the molar flow ratio of the indium source to the tin source is 4:1-100:1, the molar flow ratio of the indium source to the oxygen source is 1:550-1:5500, and the growth thickness is 40-500 nm.
2. The method for preparing a transparent electrode according to claim 1, wherein: the growth substrate material contains a nitride group.
3. The transparent electrode preparation method according to any one of claims 1 to 2, characterized in that: the indium source is trimethyl indium;
the tin source is a tetra/dimethylamino tin, tetraethyl tin, dimethyl tin or tetraphenyl tin organic tin source.
4. The method for preparing a transparent electrode according to claim 3, wherein: the oxygen source is oxygen, nitrous oxide, water or ozone.
5. The method for preparing a transparent electrode according to claim 3, wherein: the molar flow ratio of the indium source to the tin source is 4:1-100:1, and the growth time is 6-60 seconds.
6. The application of the ultraviolet light-emitting diode transparent electrode is characterized in that: the transparent electrode is used as a transparent electrode layer of the nitride ultraviolet LED with the light-emitting wavelength of 300-420 nm.
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| CN201711052464.7A CN107706278B (en) | 2017-10-30 | 2017-10-30 | Preparation method and application of transparent electrode of ultraviolet light-emitting diode |
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| CN201711052464.7A CN107706278B (en) | 2017-10-30 | 2017-10-30 | Preparation method and application of transparent electrode of ultraviolet light-emitting diode |
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| CN107706278A CN107706278A (en) | 2018-02-16 |
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