TW200921930A - Transparent conductive layer of GaN based led chip and manufacturing method thereof - Google Patents

Abstract

A transparent conductive layer (6) of a GaN based LED chip comprises a one of Al, In and Ga doped ZnO transparent conductive layer (6) formed on a P-type GaN layer (5). The method of manufacturing the transparent conductive layer (6) comprises the following steps: (A) rinsing chemically a epitaxial wafer of the GaN based LED outside of a furnace; (B) rinsing at a high temperature in a MOCVD reactive furnace; (C) using Ar gas as carrier gas, inputting oxygen, Zn, and one of Al, In and Ga metal, controlling mol rate of oxygen and Zn to 100-400:1, controlling mol rate of Zn and the metal to 3~16:1, growing the transparent conductive layer (6) on the P-type GaN layer (5); (D) annealing the transparent conductive layer (6).

Description

200921930 IX. Description of the Invention: [Technical Field] The invention relates to the field of semiconductor electronic material growth, and in particular to a disordered gallium-based light-emitting diode wafer transparent conductive layer and a manufacturing method thereof. [Prior Art] At present, the material of the transparent conductive layer of the gallium nitride-based light-emitting diode is mainly Ni/Au, copper tin oxide (ττπ, λτ. /ΑΑ). The V% of the transparent conductive layer made by Nl/Au is good, the resistivity is 1 ] 5 ^ ^ ^ 勹丄χ ιυ Ω .cm , but the visible light transmission is 4 inches poor, and the light transmittance is only 79%; IT〇 requirements , its resistivity! X coffee can also meet the industry's electricity, Wu Feng 1 X 10 Ω.cm, visible light transmittance is greater than 95% 'but ΙΤ 0 敎 and on the heat - gambling::, 乂 and right first - polar working environment " The resistance of the ions is poor, resulting in poor stability of the light-emitting diode. SUMMARY OF THE INVENTION In view of the above, the main object of the present invention is to provide a transparent conductive layer of a diode chip and a manufacturing method thereof, and improve the light transmittance in the light range while improving the light emitting diode chip. For its, the technical solution of the present invention is realized as follows: The thickness of the transparent conductive layer on the germanium layer is greater than or equal to 5 = 5000 angstroms. Tianhe j Yu Temple at 200921930 where the 'metal oxide doped with the ZnO thin film is Αι, 化 or 。. In order to improve the light transmittance and conductivity of the transparent conductive layer and the stability of the light emitting diode wafer, the thickness of the transparent conductive layer is preferably 1500 Å or more and 3800 Å or less. A method for fabricating the transparent conductive layer of the gallium nitride-based light-emitting diode wafer generally comprises the following steps: (1) subjecting the epitaxial wafer of the gallium nitride-based light-emitting diode to chemical cleaning outside the furnace;

^) The epitaxial wafer of pure gallium-based light-emitting diode is placed in a metal-organic:::mesh deposition (M_) in the reactor. 'In the reaction _ force is greater than the seek and less than or equal to 20 Torr, the temperature is greater than or equal to 45G ΐ and less than or equal to 750. 〇The speed of the graphite disc carrying the epitaxial wafer is greater than or equal to the condition of the shed and the like. The surface of the graphite material is cleaned. The cleaning time is more than 4 to 3 mm and less than or equal to 3Qmin. Chemical cleaning and high ice are used to clean the epitaxial surface. And improve I / month /

Long preparation; lower-step film production (3) in the M0CVD reactor pressure is greater than but care, the temperature is greater than or equal to the sign and less than equal and less than the J speed is greater than or equal to lion turn / min, with argon as the carrier circle Zn, oxygen, and a caged two a person Yangshuo raft, the ratio is 100~400: !, 汾盥^一^人' oxygen and the molar fraction of the W group of the second group of metals Ρ : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : Ga Ga Ga Ga Ga Ga Ga Ga Ga Ga Ga Ga Ga Ga Ga Ga Ga Ga Ga The pressure in the M0CVD reactor is greater than or equal to 5 Torr and 々, at 20 Torr, the temperature is greater than or equal to 400 °C and less than or equal to 6 〇〇, and the rotation speed of the stone is equal to or greater than 400 #/min, with argon as the load. Gas strip: It is expected that the conductive layer is post-growth annealing treatment, and the annealing treatment time is greater than or equal to 2 min and less than or equal to 3 〇 min. Wherein: the pressure of the reaction furnace in step (2) is greater than or equal to 7 Torr and less than or equal to 14 Torr, and the temperature in the step (2) is greater than the material 5 〇〇 ^ and small, at ' equal to 65 〇 C, the step ( 2) The cleaning time is greater than or equal to & less than or equal to 10min; the pressure in the reaction furnace in step (3) is greater than or equal to 7 Torr and less than or equal to 14 Torr, and the temperature in step (3) is greater than or equal to 475. 255 C or less, the flow rate of the argon gas in the step (3) is greater than or equal to 〇. 2 mol / min and less than or equal to 〇. 5m 〇 l / min; the pressure of the reactor in the step (4) is greater than or equal to 7 Torr and 2摩尔/分钟和小于等于。 5mol/min and less than or equal to 〇. 5mol, the temperature in the step (4) is greater than or equal to 475 ° C and less than or equal to 585 t, the flow rate of the argon gas in the step (4) is greater than or equal to 〇. 2mol / min and less than or equal to 〇. 5mol /min, the annealing treatment time in the step (4) is greater than or equal to 5 min and less than or equal to i〇min; the molar ratio of oxygen to zinc in the step (3) is 157 to 348:1; zinc and the first The molar fraction of the tri-family metal is for ~丨丨:1; wherein the third-group metal is Al, In or Ga. The higher the thickness of the Zn film grown on the epitaxial wafer, the more uniform, but considering the actual motor power, steps (2), 7 200921930 () spear (4) select the speed of the graphite disk 摞 A / min and Less than or equal to 9〇〇 revolutions/min. ... is greater than or equal to Xianyu, and the method of metal organic chemical vapor deposition is used to carry out the transparent conductive layer of Z0 erbium-geran tri-metal, / go to 仃zn〇 Sub-beam epitaxy, pulsed laser deposition, atomic layer' is used to carry out the growth of the transparent conductive layer. The side of the radiant or radiant is compared with the prior art, the z produced by the present invention

Ga's transparent guide two @4本隹Al, in or 込込¥ private layer, its resistivity is less than 7 χ, the transmittance is greater than θ§ _ mountain L2 cm 'in the visible light conductivity and transparent transparent conduction The layer has a fine body (4) and, because Zn〇 and (4) have matched crystal slaves, structures, and structures, it is not suitable for the ί ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ It is very strong, so that the stability of the light-emitting diode in which ZnQ is doped with ytterbium and ytterbium as a transparent conductive layer is high. 〆【Embodiment】 Example 1 'Long No.® is a transparent conductive layer of a nitride-based light-emitting diode wafer: FIG. 2 is a gallium nitride-based light-emitting diode according to the present invention. The method for fabricating a fine-grained transparent conductive layer generally comprises the following steps: (1) performing an external chemical cleaning of the epitaxial wafer of the GaN-based light-emitting diode; 1 (2) extending the epitaxial layer of the GaN-based light-emitting diode The sheet was placed in a M〇CVD reactor, and the surface of the epitaxial wafer was cleaned for 3 min at a pressure of 5 Torr, a temperature of 450, and the speed of the graphite disk carrying the epitaxial wafer was rev/min. Prepare the surface of the epitaxial wafer to clean and change the step film growth; The surface is the next (3) The pressure in the M0CVD reactor is 5 Torr, the temperature is °c, the rotation speed of the graphite disk is side-turning /-, and the molar flow ratio of the argon flow rate is 2:1 is 3:1. The actual oxygen flow is 0·06iD〇l/niin, the Zn's inflammatory η c ·, η9『 + , the inside is 〇·6_ο1/coffee, the flow rate of Α1 is two 2:,, in? Type (4) layer on the surface of the growth _ _ _ electric layer, its thickness is 500 angstroms; Temple (= ^ _ reactor pressure is 5 Torr, temperature is side c, graphite disk rotation speed is side / min, argon flow Under the condition of 0.2m〇1/_, the doped A1 transparent conductive layer is subjected to post-growth annealing treatment 2-, and the crystal lattice points are rearranged by using heat to increase the stability of the ZnO doped A1 transparent conductive layer and Conductivity. Embodiment 2 1. The method for coating a transparent conductive layer of a gallium nitride-based light-emitting diode according to the present invention generally comprises the following steps: (1) an epitaxial wafer of a GaN-based light-emitting diode Performing chemical cleaning outside the furnace; 2 Putting the epitaxial wafer of the GaN-based light-emitting diode into the shame cVD reactor, the pressure in the reaction furnace is 9·2 Torr, the temperature is 53 〇, and the stone of the cake is extended. After the disk rotation speed is 75 rpm, the epitaxial wafer is surface-cleaned for 5 min to clean the surface of the epitaxial wafer and improve the surface energy for the next film growth; 200921930 (3) The pressure in the M0CVD reactor is 9 2 Torr, the temperature is coffee. °, the speed of the graphite disk is 750 rev / -, the flow rate of argon gas is o.35m 〇 1 Under the condition of min, the molar ratio of oxygen to helium is 285.7: 1, the molar ratio of Zn to A1 is 8.75: 丨, the actual oxygen flow is 0. 05 mol/min, and the flow rate of Zn is 〇. 175mmQl /min,ai (4)Quantity ^ 02—· 'The growth of Zn〇 doped ai transparent conductive layer on the surface of the P-type GaN layer is 2500 angstroms thick; (4) The pressure in the M0CVD reactor is 9.2 Torr, and the temperature is 52. 〇C °C 'The speed of the graphite disk is 750 rev / min, and the flow rate of nitrogen is 0.35 m 〇 l / min. The Zn 〇 doped M transparent conductive layer is post-growth and annealed for 5 min. Grid dot rearrangement for increasing the stability and conductivity of the ZnO-doped A1 transparent conductive layer. Embodiment 3 The method for fabricating the gallium nitride-based light-emitting diode wafer transparent conductive layer of the present invention generally includes the following Steps: 〖 (1) The epitaxial wafer of the GaN-based light-emitting diode is subjected to chemical cleaning outside the furnace; (2) the epitaxial wafer of the GaN-based light-emitting diode is placed in a reactor of M〇CV]), in the reaction furnace The pressure is 20 Torr, the temperature is 750, and the speed of the graphite disc carrying the outer sheet is 9 rpm/min. The epitaxial wafer is surface-cleaned for 30 minutes to clean the surface of the epitaxial wafer and improve the surface energy for the next film growth; (3) the pressure in the M0CVD reactor is 2 Torr, the temperature is 6 〇 QC, and the speed of the graphite disk is At 900 rpm, the argon flow rate is 200921930 0.5 m〇l/min, the molar ratio of oxygen to Zn is 400:1, and the molar ratio of 2n to A1 is 16: 丨, actual oxygen' The soil is 0. 032m〇l/min, the flow rate of Zn is 〇. 〇8_1/min, and the amount of M white is 0. 005_i/_, Zn〇A is grown on the surface of the P-type GaN layer; The thickness is 5000 angstroms; the monthly (4) pressure in the MOCVD reactor is 2 Torr, the temperature is _ C 'the speed of the graphite disk is 900 rev / _, and the argon flow rate is 0.5 m 〇 l / min. The Zn〇-doped A1 transparent conductive layer is post-annealed for 30 min, and the crystal lattice is re-used by heat, used to increase the stability of the ZnO doped A! transparent conductive layer and the nitridation of the present invention. The gallium-based light-emitting diode daily manufacturing method generally includes the following steps: “ washing of s; (1) performing epitaxial wafer of _based light-emitting diode External chemical cleaning (2) The epitaxial wafer of the GaN-based light-emitting diode is placed in the furnace, the bunk force of the reaction furnace is 7 Torr, the temperature is 5 〇〇t, and the rotation speed of the stone is _ rev / _. Next, the epitaxial wafer is surfaced; 2 wash 6_' to clean the surface of the epitaxial wafer and improve the surface: preparation; thickening growth (3) in _1) the reactor's force is 7 torr, the speed of the graphite disc For _ _ / /, argon gas flow ^ oxygen and corrected molar ratio of 7: actual oxygen flow 200921930 is 0. 0495mol / min ' Zn flow rate is 〇 315mmol / min, A1 flow is 0 · 045 mmol/min, a Zn〇-doped M transparent conductive layer was grown on the surface of the p-type GaN layer to a thickness of 1500 angstroms; (4) the pressure in the M0CVD reactor was 7 Torr, and the temperature was 475 ° C. The rotation speed is 800 rpm, and the argon gas flow rate is 0.33 m〇l/min. The Zn〇-doped M transparent conductive layer is post-growth-treated for 6 min. By using heat, the crystal lattice points can be rearranged for increase. Stability and conductivity of ZnO doped A1 transparent conductive layer. Embodiment 5 The method for fabricating a transparent conductive layer of a gallium nitride-based light-emitting diode according to the present invention generally comprises the following steps: (1) subjecting an epitaxial wafer of a GaN-based light-emitting diode to chemical cleaning outside the furnace; 2) The epitaxial wafer of the GaN-based light-emitting diode was placed in a reaction furnace at a pressure of 14 Torr at a temperature of 65 Torr. . , the rotation speed of graphite is 7GG rev / min condition τ, the epitaxial wafer is surface cleaned lOnnn, the surface of the epitaxial wafer is cleaned and the surface energy is improved to prepare for the lower length; the sleep (3) dust force in the M0CVD reactor is 14托, the temperature is Na c 'graphar disk rotation speed · # / min, argon flow rate is 〇.5m〇i / mn, the ratio of oxygen to the molar ratio of 348: Bu Z_A1 Mo The ratio of parts is 11: i, the actual oxygen production is 0. 02 years 1 her, the flow rate of Ζη is 〇. 〇575mm〇1/min, αι的产旦^里0. 00—_ 'in the P-type GaN layer Growth on the surface _ doping ^ through 12 200921930 conductive layer, its thickness is 3800 angstroms; (4) the pressure in the M_reactor is 14 Torr' temperature is 58 °c 'the speed of the graphite disk is 7 〇〇 # special /min, the flow rate of chlorine gas is 0.5mol/min, the Zn〇-doped A丨 transparent conductive layer is 彳 post-annealed H), by using heat to make the crystal (4)__ long for increasing ZnO doping A1 transparent Stability and electrical conductivity of the conductive layer. The second figure is a schematic diagram of a structure in which a ZnO doped A1 transparent conductive layer is grown on a p-type layer of an epitaxial wafer of a GaN-based light-emitting diode; an epitaxial wafer: a sapphire substrate 1, a low-temperature gallium nitride transition layer 2 The N-type GaN layer 3, the indium/gallium nitride layer 4, and the P-type GaN layer 5 are composed of a ZnO-doped A1 transparent conductive layer 6 grown on the p-type coffee layer 5^. Embodiment 6 The method for fabricating a transparent conductive layer of a gallium nitride-based light-emitting diode wafer according to the present invention generally includes the following steps: (1) subjecting an epitaxial wafer of a GaN-based light-emitting diode to chemical cleaning outside the furnace; (2) The epitaxial wafer of the GaN-based light-emitting diode was placed in a reactor of M〇CV]). The pressure in the reactor was 20 Torr, and the temperature was 75 Torr. 〇, the speed of the black disc is 900 rev / min, the surface of the epitaxial wafer is ', first, first 30 min, so that the surface of the epitaxial wafer is cleaned and the surface energy is improved to prepare for the next film growth; ^ ' 3的氧氧与zn The pressure in the M0CVD reactor is 2 Torr, the temperature is 6 〇〇 ° C, the speed of the graphite disk is 900 rpm, and the argon flow rate is 0. 5mol/min. The molar ratio of the mole fraction is 13 200921930 400 : 1, the molar ratio of Zn to In is 16::, the actual denier is 0. lmol / min, the flow rate of Zri is 2 · 5mm 〇 1 / min, the flow rate of In is 0· 156mmol/niin, a ZnO-doped In transparent conductive layer is grown on the surface of the P-type GaM 厗矣t main layer, and its thickness is 5 Å; (4) The pressure in the M0CVD reactor is 2〇托, the temperature is _ C 'graphar disk rotation speed is 900 rev / min ' argon gas flow rate is /.5m 〇 l / min, the Zn 〇 doped In transparent conductive layer for post-growth annealing treatment 3Gmin, through The heat can be used to rearrange the crystal lattice points for increasing the stability and conductivity of the ZnO-doped In transparent conductive layer. Example 7 Nitrogen of the present invention The method for fabricating a transparent conductive layer of a gallium-based light-emitting diode wafer generally includes the following steps: (1) performing an external chemical cleaning of the epitaxial wafer of the GaN-based light-emitting diode; (2) GaN-based light-emitting diode The epitaxial wafer was placed in a m〇cvd reaction furnace. After the pressure of the reactor was 5 Torr, the temperature was 45 〇, and the rotation speed of the graphite disk was 400 rpm, the epitaxial wafer was subjected to surface J washing for 3 min to cause epitaxy. The surface of the sheet is cleaned and the surface energy is improved to prepare for the next thinning; (3) the pressure in the M0CVD reactor is 5 Torr, the temperature is on the side °c, the rotation speed of the graphite disk is 働/min, and the argon flow rate Under the condition of 0.2m〇l/min, the flow ratio of oxygen to helium is 丨〇〇: 1, the flow ratio of Zn to In is 3: 丨' actual oxygen flow rate is 0·018mol/min, Zn The flow rate is 〇. i8mmol/min, the flow rate of In is 14 200921930 0 06mniol/min, and β is in p, , = Λ

The Zn0 doped dielectric layer on the surface of the cadaveric cadmium layer has a thickness of 500 angstroms; V (4) has a pressure of 5 Torr in the M0CVD reactor, and the temperature is the rotational speed of the instrument. Dedicated/min, nitrogen flow rate is Οϋ/πΰη, the ZnQ doping_ming conductive layer is post-annealed 2mln, and the crystal lattice points can be rearranged by using heat to increase the stability of ZnO doped In transparent conductive layer. Sex and conductivity. Embodiment 8 The method for fabricating a transparent conductive layer of a gallium nitride-based light-emitting diode according to the present invention generally comprises the following steps: (1) subjecting an epitaxial wafer of a GaN-based light-emitting diode to chemical cleaning outside the furnace; 2) placing the epitaxial wafer of the GaN-based light-emitting diode into the ship's reaction furnace, where the dust force in the reactor is 7 Torr, the temperature is 5 〇〇t, and the speed of the graphite disk is 600 rpm. Surface cleaning of the epitaxial wafer 5nun 'to clean the surface of the epitaxial wafer and improve the surface energy for the next step - film growth; (3) the pressure in the M0CVD reactor is 7 Torr, the temperature is still °c 'the speed of the graphite disc For the coffee #/min, the nitrogen flow rate is 〇. 27-, the ratio of the molar ratio of oxygen to the gas is (5): 1 'the molar ratio of the coffee is 7: 1, the actual oxygen flow is 0. 0493m〇l/min ' The flow rate of Zn is 〇. 314 〇 1/_, & the flow rate is 0448 〇 l / min, growth on the surface of the p-type GaN layer doped in transparent conductive layer 'the thickness is 1500 angstroms; 15 200921930. (4) Doping ZnO in a M0CVD reactor with a pressure of 7 Torr, a temperature of 々π °c, a rotational speed of the graphite disk of _ rev / min, and an argon flow rate of 〇.27 m 〇 1 / min. The In transparent conductive layer is post-growth-treated for 5 inin, and the crystal lattice points are arranged by heat, thereby increasing the stability and conductivity of the ZnO-doped transparent conductive layer. Embodiment 9 A method for fabricating a transparent conductive layer of a gallium nitride-based light-emitting diode wafer according to the present invention generally includes the following steps: (1) performing epitaxial wafer removal of a GaN-based light-emitting diode (2) The epitaxial wafer of the GaN-based light-emitting diode is placed in a mocvd retort furnace, and the pressure in the reactor is 14 Torr, the temperature is 65 〇〇c, and the rotation speed of the graphite circle is 800 rpm. The epitaxial wafer was surface-cleaned for 1 Omin to clean the epitaxial wafer surface and improve the surface energy for the next film growth; (3) The pressure in the M0CVD reactor was 14 Torr and the temperature was 585. (:, the speed of the graphite disk is 800 rev / min, the flow rate of argon gas is 0. 375mol / min, the flow ratio of oxygen to zn is 348 : 1 ' The flow ratio of Zn to In is 11 : 1 The actual oxygen flow rate is 0. lmol / min, the flow rate of Zn is 〇. 287mmol / min, the flow rate of In is 0. 026mmol / inin, the ZnO doped In transparent conductive layer is grown on the surface of the P-type GaN layer, the thickness thereof 3800 Å; (4) The pressure in the M0CVD reactor is 14 Torr, the temperature is 585 ° C, the speed of the graphite disk is 800 rpm, and the flow rate of argon gas is 16 200921930 0. 375 m 〇 1 min. Zn 〇 ί ί 透明 transparent anneal treatment] Omin, by using 埶 二 仃 k 仃 growth for increasing the stability of ZnO doped In transparent conductive layer (9), Example 10 produced = Ming = = gallium based light The method for fabricating the transparent conductive layer of the polar body wafer generally comprises the following steps: a 7 washing; (1) performing epitaxial wafer removal of the epitaxial wafer of the GaN-based light-emitting diode (;), placing the epitaxial wafer of the GaN-based light-emitting diode Into the furnace, the pressure in the reactor is (10), the temperature is _. 〇, Shihei 2: the speed is 800 rev / min, the outside Extend the surface for 8 min to make the surface of the epitaxial wafer clean and improve the surface energy for the preparation of the lower part; keep the pancreas growing. (3) The pressure in the M0CVD reactor is +1 ° Torr, the temperature is 575 °C 'The speed of the graphite disc For _# /min, the argon flow rate is (Umol/min, the molar ratio of oxygen to the condition is 270: 1, the molar ratio of Zn to yttrium is 9: 2, the actual oxygen flow rate 0. 081m〇l/min, the flow rate of Zn is 〇. 3mm〇1/min, & the flow rate is 0. 033 leg ol / nun, the growth of Zn 〇 doped than the transparent conductive layer on the surface of the p-type GaN layer , the thickness is 3000 angstroms; (4) the pressure in the M0CVD reactor is η Torr, the temperature is 575 °c 'the rotational speed of the graphite disk is the outline #/min, and the blast flow rate is 0.4 m〇l/min. The Zn〇-doped In transparent conductive layer is post-growth-treated for 8 min, and the crystal lattice points are rearranged by using heat, and 17 200921930 is used to increase the stability and conductivity of the ZnO-doped In transparent conductive layer. Schematic diagram of p-type ZnQ-doped In transparent conductive layer of epitaxial wafer of GaN-based light-emitting diode; epitaxial wafer _ = stone base 1, low GaN buffer layer 2, NSGaNw, steel ^ /! 4 ,? hog arbitrary type luminescent layer (layer 5 ^, h in the p-type layer grown ⑽ doped ZnO transparent conductive layer 7. In Example 11 θ

The transparent conductive manufacturing method of the gallium nitride-based light-emitting diode wafer according to the present invention generally comprises the following steps: (1) performing an external chemical cleaning of the epitaxial wafer of the GaN-based light-emitting diode (2) The epitaxial wafer of the GaN-based light-emitting diode is placed in the reaction furnace, and the force in the reaction furnace is 5 Torr, and the temperature is . c, the surface of the epitaxial wafer is cleaned for 3 min under the condition of a rotating speed of 400 rpm, so that the surface of the epitaxial wafer is cleaned and the surface energy is improved to prepare for the next film growth; ' (3) in the M0CVD reactor The pressure is 5 Torr, the temperature is 4 〇〇C, the rotation speed of the graphite disk is 4 〇〇 rpm, and the argon flow rate is (Umol/min, the ratio of the oxygen to the added molar ratio is 100 The molar ratio of Zn to Ga is 3: i, the actual oxygen flow i is 0.03 mol/m; in, the flow rate of Zn is 〇·3_i/min, and the flow rate of Ga is O.lmniol/niin, A Zn〇-doped transparent conductive layer is grown on the surface of the P-type GaN layer to a thickness of 500 angstroms; (4) the pressure in the M0CVD reactor is 5 Torr, and the temperature is 4 〇〇18 200921930 C 'the speed of the graphite disk is 400 rev / min, argon gas flow rate of 0.2 m 〇 l / min, Zn0 doped Ga transparent conductive layer for post-growth annealing treatment for 2min, by using heat to make the crystal lattice point ^ to increase ΖηΟ doped Ga Stability and electrical conductivity of the transparent conductive layer. Embodiment 12% Transparent conductive production of gallium nitride based light-emitting diode wafer according to the present invention The method generally comprises the following steps: 曰f. (1) subjecting the epitaxial wafer of the luminescent diode to an external chemical cleaning; (2) placing the epitaxial wafer of the GaN-based luminescent diode into the m〇cvd reaction In the furnace, under the condition that the pressure of the reaction furnace is 20 Torr, the temperature is 75 〇t, and the rotation speed of the stone is 900 rpm, the epitaxial wafer is subjected to surface 2: two preparations to clean the surface of the epitaxial wafer and improve the surface energy. - Step;; Membrane. (3) In the coffee reactor _ force for the support, the temperature is _ C 'graphar disk rotation speed is _ rev / _, argon flow rate is 〇.5m 〇 1 / min @ conditions, The ratio of oxygen to (four) mole fraction is shed: the molar ratio of MGa is 16::, the actual amount is 0. 〇54·1/ιηιη, the flow rate of Zn is 〇. 135 fine 〇 1 field, ^ Jidan 1 0. 0084mmol/min, in p all GaN Μ this; L 丄 claw in

#层层Ζ grown ΖηΟ doped GaifM conductive layer, its thickness is 5000 angstroms; a transparent (4) in the MOOT) reactor is 2 Torr, the temperature is C' graphite disk rotation speed, turn Under the condition that the gas flow is 〇___, the Zn〇-doped transparent conductive layer is grown 19 200921930 post-annealing for 30 min, and the crystal lattice points are rearranged by using heat to increase the ZnO doped Ga transparent conductive layer. Stability and conductivity. Embodiment 13 A method for fabricating a transparent conductive layer of an emulsified gallium-based light-emitting diode according to the present invention generally comprises the following steps: (1) performing an external chemical cleaning of an epitaxial wafer of a GaN-based light-emitting diode; The epitaxial wafer of the GaN-based light-emitting diode is placed in a reaction furnace, and the epitaxial wafer is surface-cleaned under the condition that the pressure of the reaction furnace is 7 Torr and the temperature of the graphite disk is _rpm/πΰη. 5min, make the surface of the epitaxial wafer clean and prepare for the pen; "The surface energy of the surface can be grown for the next-step film. ("The pressure in the coffee reactor is 7 Torr, and the temperature is still C'. #/_, under the condition of nitrogen flow rate of 0.4mol/niin, the molar ratio of λ ga· p 157.彳71 to the emulsion and & is 157.1, and the molar ratio of Ζη to (4) is 7: The amount of Bu is 0·05mol/min, and the machine of k . Ζ 的 is 0. 31δ_/−, the flow of Ga is on the surface of the P-type GaN layer: conductive layer, Its thickness is 1500 angstroms; L-tan Ga is transparent (4) in the M0CVD reactor, the force is °C, the speed of the graphite disk is _ 474, the condition == n The argon flow rate is post-annealed to the 5 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Gallium nitride-based luminescence-God 0 manufacturing method generally includes the following steps: - washing of the transparent conductive layer of the 曰曰 film; (1) epitaxial wafer of the W (four)-based light-emitting diode is performed outside the furnace (on: The epitaxial wafer of the base light-emitting diode is placed in the furnace, and the dust force in the reaction furnace is 14 Torr, and the temperature is sir, : 'The rotational speed is 750 rpm, and the epitaxial wafer is subjected to surface 1 Omin to make the epitaxy The surface of the sheet is cleaned and prepared for long-term changes. The surface is the lower-step film produced by t2? The reaction furnace is deleted to 14 Torr, the temperature is coffee C, the speed of the graphite 0 disk is 750 rpm, argon gas. The flow ratio is 〇34387-7, the molar ratio of oxygen to & is 3 strokes _ 1, the molar ratio of Zn to Ga is „ :丨, the actual amount is 0· _m〇1/min The flow rate of Zn is 〇. 247mm〇i/mi is two, .1/_' is grown on the surface of _ layer 』:: conductive layer, its thickness 3800 angstroms; (4) 14 in the _D reactor, the temperature is Na, the speed of the graphite disk is 750 #/ffiin, and the flow rate of argon is 375.375m〇l/min. The Zn〇 is doped with a transparent conductive acoustically and post-annealed to treat the η, and by using heat, the crystal lattice point is used to increase the stability and conductivity of the 透明ηΟ-doped Ga transparent conductive layer. Embodiment 15 A method for fabricating a transparent conductive layer of a gallium nitride-based light-emitting diode according to the present invention 21 200921930 generally includes the following steps: (1) performing an external chemical cleaning of an epitaxial wafer of a GaN-based light-emitting diode (2) The epitaxial wafer of the GaN-based light-emitting diode is placed in an M〇CVD reactor. The temperature in the reactor is 10 Torr, and the temperature of the graphite disk is 800 rpm. Under the condition, the epitaxial wafer is surface-cleaned for 7 minutes to make the surface of the epitaxial wafer clean and improve the surface energy for the next film growth; ' ^ (3) The pressure in the MOCVD reactor is 1 Torr, and the temperature is 57 〇C ' When the rotation speed of the graphite disk is 800 rpm, and the flow rate of the atmosphere is 0.3 mol/min, the molar ratio of oxygen to Zn is 123: 1, and the molar ratio of Zii to Ga is 9: ' The actual oxygen flow rate is 0. 024mol/min ' The flow rate of Zn is 〇. 195mmol/min, and the flow rate of Ga is 0·0217mmol/min. The Zn0-doped Ga transparent conductive layer is grown on the surface of the P-type GaN layer, and the thickness thereof is 2500 angstroms; (4) The dust force in the MOCVD reactor is 1 Torr, and the temperature is wo °C 'Graphite disc The ZnO doped Ga transparent conductive layer was post-growth-treated for 7 min at a rotation speed of 800 rpm and an argon flow rate of 0.3 mol/min. The crystal lattices were rearranged by heat to increase the ZnO doping. Stability and conductivity of the hetero-Ga transparent conductive layer. The fourth figure is a schematic view showing the structure in which a ZnO-doped In transparent conductive layer is grown on the p-type layer of the epitaxial wafer of the GaN-based light-emitting diode. The epitaxial wafer is composed of a sapphire substrate 1, a low-temperature gallium nitride transition layer 2, an N-type GaN layer 3, an indium gallium germanium/gallium nitride light-emitting layer 4, and a p-type GaN layer 5, and is grown on the P-type GaN layer 5 on 22 200921930. : Widely doped Ga transparent conductive layer 8. The invention adopts the growth of the metal layer, and can also adopt the method of: transparent conductive atomic layer epitaxy, sputtering or latitude, pulsed laser; redundancy and growth. The method realizes the (b) conductive layer of the p-type voiced transparent conductive layer of the GaN-based light-emitting diode epitaxial wafer, and then the θ is longer than the (fourth)-based light-emitting/polarizing film. In the five figures, the 曰 加工 导电 导电 导电 , , , 尤 尤 尤 尤 尤 尤 尤 0 0 0 0 0 0 0 0 0 0 0 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四The electrodes 9 are connected to each other, and the _GaN layer is connected to the N (four). The second and second, the transparent conductive layer is a viscous, drink; Table 1 Comparison of Ni/Au, . The material of the present invention is used as the transparent conductive layer of the wafer holder 作为0 as the transparent conductive layer of the wafer light intensity and forward voltage LED size test current (mA) transparent conductive layer Iv (mcd) Vf (V) 12mil X 12mil - ---— 20 Ni/Au 43 ---- 3.17 12mil χ *— 20 ΙΤ0 54 ---- 3.21 23 200921930 12mil —.. ——_ 12rail x 20 ZnO doped 12mil A1 60 3.28 12mil x 20 ZnO Miscellaneous - 12mil In 58 3.31 ν' 12mil x 20 ZnO doping ———. 12mil Ga 56 3.29 Table 1 The data shown in Table 1 is the result of testing with the same standard, 帛LED photoelectric characteristics meter. As shown in Table 1, the wafer size is 12 mil x 12 mil, and the present invention uses Zn 〇 doped A1, Zn 〇 doped In or ZnO # hetero Ga as the light intensity of the transparent conductive layer under the condition of a current of 20 mA. The light intensity of the transparent conductive layer was increased by m, 7.4%, and 3.7%, respectively, by $6〇mcd, 58mcd, and 56mcd'. The invention uses Zn〇 doped A1, Zn〇-doped In or ZnO doped Ga as the forward voltage of the transparent conductive layer and the forward voltage phase of the transparent conductive layer with ^Ni/Au, ΙΤ0 as the industry requirement. 5V. 'Test the wafer made of ZnO doped A1 transparent conductive layer, the test method is bare crystal (four), the light intensity is 119mcd Γ 24 200921930 The wafer is continuously operated under 20 mA conditions after iqoq hours 'light intensity For 114mcd, the light decay is 4.2%. The reliability test was performed on a wafer made of ZnO doped In transparent conductive layer. The light intensity before the test was ll 〇 mcd, and the wafer was continuously operated for 1000 hours under the condition of 2 mA. The light intensity was 104 mcd, and the light was decayed. It is 5.4%. The reliability of the wafer made of ZnO doped Ga transparent conductive layer was tested. Before the test, the light intensity was l〇2mcd. After the wafer was operated for 20 hours under the condition of 20mA, the light intensity was 96mcd and the light decay was 5. 9%. In summary, the transparent conductive layer of ZnO doped Al, In or Ga of the present invention has good light transmittance, and the wafer made of the transparent conductive layer of A1, In or Ga is doped with the Zn 〇. The light decay after 1 hour is less than 1%, indicating that the stability of the light-emitting diode in which a third group metal is doped with ZnO as the transparent conductive layer is high. The above description is only a preferred embodiment of the present invention and is not intended to limit the scope of the present invention.

25 200921930 [Simplified description of the drawings] The first figure is a flow chart for fabricating a transparent conductive layer of a gallium nitride-based light-emitting diode of the present invention; 曰 The second figure is a GaN-based light-emitting diode epitaxial wafer of the present invention. Schematic diagram of the structure of growing ZnO-doped A1 transparent conductive layer on the type layer; the second figure is a schematic diagram of the structure of growing ZnO-doped In transparent conductive layer on the p-type bank of the GaN-based light-emitting diode epitaxial wafer according to the present invention; The structure of the present invention is a structure of growing a ZnO-doped Ga transparent conductive layer on a p-type layer of a GaN-based light-emitting diode epitaxial wafer; the fifth figure is a method for growing ZnO on a p-type layer of a GaN-based light-emitting diode epitaxial wafer according to the present invention; Schematic diagram of a wafer structure processed after doping an A1 transparent conductive layer; FIG. 6 is a schematic view showing a structure of a wafer processed by growing a ZnO-doped In transparent conductive layer on a p-type layer of a GaN-based light-emitting diode epitaxial wafer according to the present invention; FIG. 7 is a schematic view showing the structure of a wafer processed by growing a ZnO-doped Ga transparent conductive layer on a p-type layer of a GaN-based light-emitting diode epitaxial wafer according to the present invention. [Main component symbol description] 1 Sapphire substrate 2 Low-temperature gallium nitride transition layer 3 N-type GaN layer 4 Indium gallium nitride/gallium nitride light-emitting layer 26 200921930 5 P-type GaN layer 6 ZnO-doped A1 transparent conductive layer 7 ZnO doping In transparent conductive layer 8 ZnO doped Ga transparent conductive layer 9 P electrode 10 N electrode

C 27

Claims (1)

200921930 X. Patent application scope · · Gallium nitride-based light-emitting diode S The transparent conductive layer is composed of an oxide layer, which is grown on a p-type gallium nitride layer, and the transparent conductive: wide metal, Raw and less than or equal to 5000 angstroms. The gallium nitride-based light-emitting diode wafer transparent conductive layer Q described in claim 1 is wherein the third group metal is indium, indium or gallium. The monthly thickness of the electric layer is equal to or less than the simple and small electroacoustic 4:::::: the gallium nitride-based light-emitting diode wafer transparent guide two:: the transparent conductive The thickness of the layer is greater than the equivalent.埃和小光一极雕 = β-monthly method 1, 2, 3 or 4 of the method for nitriding a base sheet transparent conductive layer 'where' the method includes the following cleaning; GaN-based luminescence The epitaxial wafer of the diode is subjected to furnace chemistry, and (2) the epitaxial wafer of the gallium nitride-based light-emitting diode is placed in a metal organic chemical vapor deposition reactor, and the pressure in the reactor is greater than or equal to 5 Torr and less than or equal to 2 〇, the temperature is greater than or equal to 45 〇. 〇 and less than or equal to (10) ^, 'The speed of the two discs is greater than or equal to 4 (9) rev / min, the epitaxial wafer is ordered to be cleaned, the cleaning time is greater than or equal to 3 min and less than or equal to 3 〇 min; 28 200921930 at ":: The pressure in the metal organic chemical vapor deposition reactor is greater than or equal to 2 Torr, the temperature is greater than or equal to the shed. c and less than or equal to the carrier gas: strip: the speed is greater than or equal to 400 rev / _, with chlorine as ===: words, oxygen And a kind of Group III metal, the ratio of the molar ratio of oxygen / 砰 is 100~4nn. The ratio of the parts is: 3~16: i... The symplectic and the metal of the third group are m^μ^-- Oxidation thickness on the surface of the Ρ-type gallium nitride layer; = growth of a transparent conductive layer of a group III metal, a degree of a transparent conductive layer; a degree greater than 500 angstroms and less than or equal to angstrom; and =) in metal organic chemical vapor deposition The pressure of the reactor is greater than or equal to 2G. The temperature is greater than or equal to shed. c and less than or equal to: the speed of the two-two ink disc is greater than or equal to the revolution / min, = = the transparent conductive layer is post-growth annealing, annealing The guardian is greater than or equal to and less than or equal to 30 minutes. The gallium nitride-based light-emitting diode wafer is more permeable than the pressure of the reactor described in the step (2), and the temperature is equal to 5 GG t in step (2). And less than or equal to 65G, the time of = is greater than or equal to 5min and less than or equal to 1〇_. In the "Cleaning Conductive Si: 6", the gallium nitride-based light-emitting diode wafer is more than 7 cups, and the pressure of the reactor in the step (3) is greater than 7 Torr and less than Equal to 14 Torr, step (3) ..., equal to 5δ5., step (3), two, machine "" temple at 0. 2m〇l / min and less than or equal to 〇. 5m 〇 1 / min. Manufacture of a gallium nitride-based light-emitting diode wafer as described in θ _7, 29 200921930. The reaction force of the reactor described in the step (4) is equal to 475 ίί/, ί at 14 Torr' step (4) The temperature is large, a denier is less than the temple at 585 C, and the argon gas in step (4) is equal to 0.2 moi/min and less than or equal to 0.5 mol/min. The time is greater than or equal to 5 min and less than or equal to 10 min., , - r-4^. The oxygen and zinc in ac4 / I, the method for producing a gallium nitride-based inventive conductive layer according to claim 8 , the molar fraction ratio of the step (3) is 157 to 348: 1. If % i is the method for producing a gallium nitride-based light-emitting diode wafer μ two-conducting layer according to Item 9, wherein The molar ratio of the zinc to the brother-metal-free portion in the step (3) is 7 to 11: 1. The transparent conductive layer of the gallium nitride-based light-emitting diode wafer is prepared as described in claim 10 11 ^ , into the P, where the third group to the genus in the step (3) is aluminum, indium or gallium. The gallium nitride based fabrication as described in claim 5 The method of the photodiode wafer force month V ^ layer 'where the pressure in the step (3) is greater than or equal to 7 and less than or equal to 丨 4 Torr, and the temperature in the step (3) is greater than the equal furnace v > ^, it is as claimed in claim 12, α, it is less than or equal to 585. (:, the amount of argon gas in step (3) is greater than or equal to 0. 2m〇l / min and less than or equal to 〇. 5mol / min. The method for fabricating a GaN-based light-emitting diode wafer, wherein the pressure of the reactor in the step (4) is greater than or equal to 7 Torr and less than or equal to 14 Torr, as described in the step (4). The temperature is greater than or equal to 475 t: and less than or equal to 585. The flow rate of the argon 30 200921930 gas in the step (4) is greater than or equal to 0.2 m〇l/min and less than or equal to 〇. 5 mol/min, as described in the step (4). The annealing time ί is greater than or equal to 5 min and less than or equal to 10 min. The method of producing a transparent conductive layer of a gallium nitride-based light-emitting diode wafer according to claim 13, wherein the oxygen in the step (3) The molar ratio of zinc to zinc is 157 to 348: 1. The gallium nitride-based light-emitting diode is fabricated as described in claim 4 a method for crystallizing a conductive layer, wherein a ratio of the mole fraction of the word in the step (3) to the metal of the tri-group metal is M1 : 1 ... the third in the base light-emitting diode wafer 3) The method of producing a gallium nitride human monthly conductive layer according to claim 15, wherein the step metal is a face, indium or gallium. The transparent conductive layer is made of aluminum, and the gallium nitride-based light-emitting diode chip is fabricated, wherein the third group in the step (3)