CN103346230A - Copper sulfide/oxide zinc radical composite transparent electrode light-emitting diode and preparation method thereof - Google Patents
Copper sulfide/oxide zinc radical composite transparent electrode light-emitting diode and preparation method thereof Download PDFInfo
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- CN103346230A CN103346230A CN2013102408805A CN201310240880A CN103346230A CN 103346230 A CN103346230 A CN 103346230A CN 2013102408805 A CN2013102408805 A CN 2013102408805A CN 201310240880 A CN201310240880 A CN 201310240880A CN 103346230 A CN103346230 A CN 103346230A
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Abstract
The invention discloses a copper sulfide/oxide zinc radical composite transparent electrode light-emitting diode and a preparation method of the copper sulfide/oxide zinc radical composite transparent electrode light emitting diode. A copper sulfide middle thin layer is used for improving ohmic contact between an oxide zinc radical LED transparent electrode and p-type gallium nitride. Compared with the situation that metal is simply used as a middle inserting layer, light transmissivity of the copper sulfide is significantly improved, and better ohmic contact can be formed between the copper sulfide and the p-type gallium nitride. The light emitting diode comprises a sapphire substrate, a buffer layer, an n-type gallium nitride, a quantum well, the p-type gallium nitride, a copper sulfide thin film, an oxide zinc radical transparent current expanding layer, a p-type metal electrode and an n-type metal electrode. The ohmic contact between the p-type gallium nitride and a zinc oxide transparent electrode layer is improved by the utilization of the copper sulfide/oxide zinc radical composite transparent electrode, and light extraction efficiency and reliability of LED chips are improved.
Description
Technical field
The present invention relates to a kind of light-emitting diode chip for backlight unit and preparation method thereof, particularly a kind of Cu oxide/Zinc oxide-base composite transparent electrode light-emitting diode and preparation method thereof.
Background technology
The luminous efficacy of LED can be up to more than the 200lm/W in theory, and present white light LEDs then has only about 100lm/W, compares with energy-saving fluorescent lamp to also have certain gap; And its price is compared with conventional light source very big inferior position is also arranged.The luminous efficiency that improves LED mainly contains two kinds of approach: the internal quantum efficiency that 1) improves led chip; 2) external quantum efficiency of raising led chip.At present, the interior quantum luminous efficiency of ultra-high brightness LED has had very large improvement, has the highlyest reached 80%, and further the space of improving is little.Therefore the external quantum efficiency that improves led chip is to improve the key of the total luminous efficiency of LED.And the GaNg of traditional structure base LED is owing to reasons such as total reflection and absorptions, and light extraction efficiency has only a few percent, and it is very big to improve the space.Led chip heating simultaneously also affects quality and the life-span of great power LED.The method of the raising LED external quantum efficiency that adopts mainly contains at present: transparent substrates technology, metal film reflection technology, surface micro-structure technology, flip chip technology (fct), chip bonding technology, laser lift-off technique etc.
Because resistivity is higher, electric current is difficult in the p-GaN diffusion into the surface and comes, thereby influences the luminescent properties of LED device.This just need be at p-GaN surface preparation layer of transparent conductive layer, and it should have higher light transmission rate and conductivity, simultaneously again and form ohmic contact preferably between the p-GaN.Be vital at the high-quality TCL of p-GaN preparation for the development of LED how.Because the p-GaN work function is bigger, and ohmic contact is difficult to form between the electrode, so GaN base LED a big chunk voltage when work can drop on the interface of p-GaN ohmic contact, this also can cause at a large amount of heat of p-GaN ohmic contact interface generation, thereby causes component failure.Improve the surface preparation technology that mainly contains, annealing technology, employing heterojunction and superlattice structure technology, the heavy doping technology etc. of ohmic contact at present.And Ni/Au based metallization and ITO transparent conductive film are the technology of comparative maturity wherein.
In recent years, adopt the ZnO conductive film of doping such as Ga, Al, In to receive increasing concern.ZnO and ito thin film have similar optics and electric property, even some aspect also is better than traditional ITO material: high light transmission rate, thermal conductivity, more mate with the GaN lattice, better chemical stability and preparation method's variation.From the environmental protection angle, ZnO does not contain phosphide material, can not pollute environment.How to improve the contact performance of ZnO and p-GaN, this impels the application of zno-based LED in lighting field for the quality, useful life and the luminous efficiency that improve zno-based LED, and is significant.Be difficult between ZnO and the p-type GaN form ohmic contact but directly adopt, because the GaN surface is easy to sustain damage, cause Schottky contacts in the ZnO deposition process.The oxide of copper all is the p-type semiconductor, has conductivity preferably, and its transmitance is better simultaneously, is more satisfactory ohmic contact material.The experiment proved that, Cu oxide is inserted between p-type GaN and the zinc oxide can significantly reduces contact resistance, realize good Ohmic contact.
Summary of the invention
The objective of the invention is to the defective at the prior art existence, a kind of Cu oxide/Zinc oxide-base composite transparent electrode light-emitting diode and preparation method thereof is provided, this light-emitting diode chip for backlight unit has improved the light extraction efficiency of large-power light-emitting diodes, increases the uniformity of p-type semiconductor layer electric current diffusion.
For achieving the above object, design of the present invention is: problems such as toxic, the complex process of the indium resource scarcity that exists at current LED, indium, improve and adopt transmitance height, good, the resourceful zinc oxide of conductive doped property as current extending, for zinc oxide current expansion and p-type gallium nitride surface formation good Ohmic contact, first evaporation layer of copper oxide skin(coating) before p-type gallium nitride surface sputtering zinc oxide film, improve ohmic contact, thereby improve LED light efficiency and reliability.
According to above-mentioned inventive concept, the present invention adopts following technical proposals:
A kind of Cu oxide/Zinc oxide-base composite transparent electrode light-emitting diode comprises Sapphire Substrate, resilient coating, n type gallium nitride, quantum well, p-type gallium nitride, Cu oxide film, zinc-oxide-base transparent current extending, p-type metal electrode and n type metal electrode; Described resilient coating, n type gallium nitride, quantum well, p-type gallium nitride are to grow successively on Sapphire Substrate in MOCVD; Described Cu oxide thin film deposition is on the surface of p-type gallium nitride; Described zinc-oxide-base transparent current expansion is deposited upon on the Cu oxide film; Described n type metal electrode connects n type gallium nitride, and described p-type metal electrode connects the zinc-oxide-base transparent current extending.
The material of described zinc-oxide-base transparent current extending is ZnO:Ga or ZnO:Al or ZnO:In.
The Cu oxide chemical formula of described Cu oxide film is Cu
xO, wherein x value scope is between 1 to 2.
The preparation method of a kind of Cu oxide/Zinc oxide-base composite transparent electrode light-emitting diode, processing step is as follows:
A) with the method for MOCVD grown buffer layer, n type gallium nitride, quantum well, p-type gallium nitride successively on Sapphire Substrate, and epitaxial wafer is carried out magnesium activate annealing in process;
B) use chemical reagent that epitaxial wafer is carried out surface treatment;
C) utilize electron beam evaporation plating or vacuum evaporation or molecular beam epitaxy deposited copper sull on the p-type gallium nitride;
D) prepare the zinc-oxide-base transparent current extending by magnetron sputtering or electron beam deposition at the Cu oxide film;
E) etch designed zinc oxide transparent conductive film figure with wet etching or dried method of carving at the zinc-oxide-base transparent current extending;
F) by argon ion etching or ICP dry etching n type gallium nitride is come out, prepare required chip structure;
G) epitaxial wafer is carried out annealing in process, reduce the contact resistance between Cu oxide film and p-type gallium nitride surface layer and Cu oxide film and the zinc-oxide-base transparent current extending on the one hand, repair etching injury on the one hand;
H) method by thermal evaporation or electron beam evaporation deposits p-type metal electrode and n type metal electrode;
I) annealing in process is again carried out the alloying of metal electrode;
J) cut apart epitaxial wafer.
Magnesium in the described step a) activate annealing temperature be 200 degree to 700 degree, annealing atmosphere is vacuum, air, nitrogen or purity oxygen.
Chemical reagent in the described step b) is that KOH or HCl or chloroazotic acid or sulfuric acid add hydrogen peroxide.
Cu oxide in the Cu oxide film in the described step c) adopts first copper steam-plating metal, metal exposed high-temperature oxydation in air or oxygen atmosphere is obtained again.
Cu oxide film thickness in the described step c) is 1 ~ 50nm.
Compared with prior art, the present invention has following outstanding substantive distinguishing features and progressive significantly:
Cu oxide/Zinc oxide-base composite transparent electrode light-emitting diode the transmitance of the present invention's preparation is higher, reduced the contact resistance of transparency electrode and p-type gallium nitride surface, formed better ohmic contact, preparation technology is simple, with low cost, the diffusion of p-type semiconductor layer electric current is more even.The reduction of the raising of efficient, the raising of reliability and cost all will promote the paces of LED illumination.
Description of drawings
Fig. 1 is the front view of light emitting diode construction figure of the present invention.
Fig. 2 is the vertical view of light emitting diode construction figure of the present invention.
Embodiment
Below in conjunction with accompanying drawing, specific embodiments of the invention are described further.
As depicted in figs. 1 and 2, a kind of Cu oxide/Zinc oxide-base composite transparent electrode light-emitting diode comprises Sapphire Substrate 1, resilient coating 2, n type gallium nitride 3, quantum well 4, p-type gallium nitride 5, Cu oxide film 6, zinc-oxide-base transparent current extending 7, p-type metal electrode 8 and n type metal electrode 9; Described resilient coating 2, n type gallium nitride 3, quantum well 4, p-type gallium nitride 5 are to grow successively on Sapphire Substrate 1 in MOCVD; Described Cu oxide film 6 is deposited on the surface of p-type gallium nitride 5; Described zinc-oxide-base transparent current extending 7 is deposited on the Cu oxide film 6; Described n type metal electrode 9 connects n type gallium nitride 3, and described p-type metal electrode 8 connects zinc-oxide-base transparent current extending 7.
The preparation method of a kind of Cu oxide/Zinc oxide-base composite transparent electrode light-emitting diode is as follows: at first, and with the method for MOCVD resilient coating 2, n type gallium nitride 3, quantum well 4, p-type gallium nitride 5 successively on Sapphire Substrate 1.And then epitaxial wafer is carried out magnesium and activate annealing in process; Use chemical reagent such as KOH or HCl or chloroazotic acid that epitaxial wafer is carried out surface treatment then; Deposit the Cu oxide film of 5nm, 10nm, 20nm or 50nm respectively at gallium nitride surface by the method for electron beam or thermal evaporation, by rf magnetron sputtering 100,200,300,400 or the zinc oxide transparent conductive film of 500nm, formed Cu oxide/Zinc oxide-base composite transparent electrode again.With the method for wet etching, the composite transparent electrode corrosion is gone out required figure, n type gallium nitride is come out the annealing in process under the line space of going forward side by side gas or the oxygen atmosphere by ion etching or ICP etching again; Method deposition n type metal electrode 9 and p-type metal electrode 8 by thermal evaporation or electron beam evaporation; At last, carry out the alloying annealing in process of metal electrode and cut apart epitaxial wafer.
Claims (8)
1. Cu oxide/Zinc oxide-base composite transparent electrode light-emitting diode comprises Sapphire Substrate (1), resilient coating (2), n type gallium nitride (3), quantum well (4), p-type gallium nitride (5), Cu oxide film (6), zinc-oxide-base transparent current extending (7), p-type metal electrode (8) and n type metal electrode (9); It is characterized in that described resilient coating (2), n type gallium nitride (3), quantum well (4), p-type gallium nitride (5) are to grow successively on Sapphire Substrate (1) in MOCVD; Described Cu oxide film (6) is deposited on the surface of p-type gallium nitride (5); Described zinc-oxide-base transparent current extending (7) is deposited on the Cu oxide film (6); Described n type metal electrode (9) connects n type gallium nitride (3), and described p-type metal electrode (8) connects zinc-oxide-base transparent current extending (7).
2. Cu oxide according to claim 1/Zinc oxide-base composite transparent electrode light-emitting diode is characterized in that, the material of described zinc-oxide-base transparent current extending (7) is ZnO:Ga or ZnO:Al or ZnO:In.
3. Cu oxide according to claim 1/Zinc oxide-base composite transparent electrode light-emitting diode is characterized in that, the Cu oxide chemical formula of described Cu oxide film (6) is Cu
xO, wherein x value scope is between 1 to 2.
4. the preparation method of Cu oxide/Zinc oxide-base composite transparent electrode light-emitting diode is characterized in that processing step is as follows:
A) with the method for MOCVD grown buffer layer (2), n type gallium nitride (3), quantum well (4), p-type gallium nitride (5) successively on Sapphire Substrate (1), and epitaxial wafer is carried out magnesium activate annealing in process;
B) use chemical reagent that epitaxial wafer is carried out surface treatment;
C) utilize electron beam evaporation plating or vacuum evaporation or molecular beam epitaxy to go up deposited copper sull (6) at p-type gallium nitride (5);
D) prepare zinc-oxide-base transparent current extending (7) by magnetron sputtering or electron beam deposition at Cu oxide film (6);
E) etch designed zinc oxide transparent conductive film figure with wet etching or dried method of carving at zinc-oxide-base transparent current extending (7);
F) by argon ion etching or ICP dry etching n type gallium nitride (3) is come out, prepare required chip structure;
G) epitaxial wafer is carried out annealing in process, reduce the contact resistance between Cu oxide film (6) and p-type gallium nitride (5) superficial layer and Cu oxide film (6) and the zinc-oxide-base transparent current extending (7) on the one hand, repair etching injury on the one hand;
H) method by thermal evaporation or electron beam evaporation deposits p-type metal electrode (8) and n type metal electrode (9);
I) annealing in process is again carried out the alloying of metal electrode;
J) cut apart epitaxial wafer.
5. the preparation method of Cu oxide according to claim 4/Zinc oxide-base composite transparent electrode light-emitting diode, it is characterized in that, magnesium in the described step a) activate annealing temperature be 200 degree to 700 degree, annealing atmosphere is vacuum, air, nitrogen or purity oxygen.
6. the preparation method of Cu oxide according to claim 4/Zinc oxide-base composite transparent electrode light-emitting diode is characterized in that, the chemical reagent in the described step b) is that KOH or HCl or chloroazotic acid or sulfuric acid add hydrogen peroxide.
7. the preparation method of Cu oxide according to claim 4/Zinc oxide-base composite transparent electrode light-emitting diode, it is characterized in that, Cu oxide in the Cu oxide film (6) in the described step c) adopts first copper steam-plating metal, metal exposed high-temperature oxydation in air or oxygen atmosphere is obtained again.
8. the preparation method of Cu oxide according to claim 4/Zinc oxide-base composite transparent electrode light-emitting diode is characterized in that, Cu oxide film (6) thickness in the described step c) is 1 ~ 50nm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110808292A (en) * | 2019-10-31 | 2020-02-18 | 中国科学院国家空间科学中心 | GaN-based completely vertical Schottky varactor based on metal eave structure and preparation method thereof |
| CN111640836A (en) * | 2020-06-18 | 2020-09-08 | 佛山紫熙慧众科技有限公司 | GaN-based LED device electrode structure and LED device |
| CN114122124A (en) * | 2021-10-21 | 2022-03-01 | 汕头大学 | Ohmic electrode and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050082557A1 (en) * | 2003-10-16 | 2005-04-21 | Samsung Electronics Co., Ltd. | Nitride-based light emitting device and method of manufacturing the same |
| CN1917245A (en) * | 2005-08-09 | 2007-02-21 | 三星电子株式会社 | Nitride-based light emitting device and manufacturing method thereof |
| CN102169943A (en) * | 2011-03-29 | 2011-08-31 | 上海大学 | Light-emitting diode (LED) with indium tin oxide (ITO)/zinc oxide based composite transparent electrode and preparation method of LED |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050082557A1 (en) * | 2003-10-16 | 2005-04-21 | Samsung Electronics Co., Ltd. | Nitride-based light emitting device and method of manufacturing the same |
| CN1917245A (en) * | 2005-08-09 | 2007-02-21 | 三星电子株式会社 | Nitride-based light emitting device and manufacturing method thereof |
| CN102169943A (en) * | 2011-03-29 | 2011-08-31 | 上海大学 | Light-emitting diode (LED) with indium tin oxide (ITO)/zinc oxide based composite transparent electrode and preparation method of LED |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110808292A (en) * | 2019-10-31 | 2020-02-18 | 中国科学院国家空间科学中心 | GaN-based completely vertical Schottky varactor based on metal eave structure and preparation method thereof |
| CN111640836A (en) * | 2020-06-18 | 2020-09-08 | 佛山紫熙慧众科技有限公司 | GaN-based LED device electrode structure and LED device |
| CN114122124A (en) * | 2021-10-21 | 2022-03-01 | 汕头大学 | Ohmic electrode and preparation method and application thereof |
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Application publication date: 20131009 |