CN103219433A - Light emitting diode and manufacturing method thereof - Google Patents
Light emitting diode and manufacturing method thereof Download PDFInfo
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- CN103219433A CN103219433A CN2012100187998A CN201210018799A CN103219433A CN 103219433 A CN103219433 A CN 103219433A CN 2012100187998 A CN2012100187998 A CN 2012100187998A CN 201210018799 A CN201210018799 A CN 201210018799A CN 103219433 A CN103219433 A CN 103219433A
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Abstract
The invention relates to a light emitting diode and a manufacturing method of the light emitting diode. The manufacturing method includes the following steps: forming a plurality of epitaxy wafer material layers on a substrate, wherein the plurality of the epitaxy wafer material layers sequentially comprise a buffer layer, an n-type semiconductor layer, a luminous layer and a p-type semiconductor layer; forming a transparent conducting layer on the upper surface of the p-type semiconductor layer; conducting roughening process on the transparent conducting layer by using the auto-oxidation etching technology to enable the transparent conducting layer to have a rough surface; and forming a plurality of electrodes. Due to the roughening process, total internal reflection can be reduced and luminous efficiency of the light emitting diode can be improved.
Description
Technical field
The present invention relates to a kind of light-emitting diode assembly and manufacture method thereof, more relate to a kind of manufacture method that comprises the light-emitting diode assembly of autoxidation etching technique roughened.
Background technology
Light-emitting diode (light emitting diode, be called for short LED) has been widely used in lighting device and display unit at present, and known production method comprises: on substrate crystalline substance, etching epitaxial layer of heap of stone, conductive layer is set and step such as electrode is set.
In recent years, the luminous efficiency of lifting light-emitting diode assembly is one of target of lasting research in present technique field and development.Compound (reducing the exterior light delivery efficiency influences light-emitting diode luminance for total internal reflection, TIR) mechanism with total internal reflection because light-emitting diode inside has complicated carrier.Therefore, problem at light output brightness, reduce light in light-emitting diode inner full-reflection rate, mainly improve, or promote luminous efficiency with special constructions such as large tracts of land assembly (large area chip), crystal covering type assembly (flip-chip), photonic crystal (photonic crystal), resonant cavity (resonant cavity) light-emitting diodes with surface roughening processing (surface roughness), the change geometry technology such as (shaping) of transparency conducting layer.
At the technology of transparency conducting layer processing procedure, known processing procedure spininess relates in tin indium oxide (Sn:In the method for transparency conducting layer being set, all not having
2O
3, ITO) surface treatment method, for example, anticipate substrate with plasma or ion beam after, form indium tin oxide layer on substrate with the crystal seed (seed) or the sputtering way of bulk (bulk) again, make indium tin oxide layer have different crystalline lattice towards.In addition, handle at indium tin oxide surfaces, what prior art was instructed is to form the method that has than the indium tin oxide layer of low roughness.All not mentioned surface roughening in known processing procedure, the then smooth surface of the easy oxidized indium tin of light reflection, the shortcoming that causes the assembly luminous efficiency to reduce.
In addition, surface roughening treatment step at conductive layer, in known processing procedure, lie in conductive layer surface covering photoresist layer and carry out etching as light shield (mask), to produce required pattern or desired structure at conductive layer surface, for example, form porous cave structure or form predetermined pattern etc., all must can reach by the shield side of specific pattern with given shape at transparency conducting layer.Known shielding material is for example azo-compound (azide compounds), phenol resin (phenol resin), phenolic resins (novolak resin), poly-methyl propionyl acid methyl esters (PMMA), poly-methyl butyl ketone (PMIBK) etc.
With regard to the processing procedure of known light-emitting diode, use the light shield of specific patternization to carry out etch processes, must carry out light shield and cover step and pattern definition step, and after etching is finished, must remove light shield, with regard to fabrication steps, still belong to loaded down with trivial detailsly, and increase the degree of difficulty of processing procedure keyholed back plate.Therefore, the improvement for the light-emitting diode processing procedure still has its demand.
Summary of the invention
In view of this, the invention provides a kind of manufacturing method for LED, comprising: form a plurality of brilliant material layers of heap of stone on substrate, these a plurality of brilliant material layers of heap of stone comprise resilient coating, n type semiconductor layer, luminescent layer and p type semiconductor layer in regular turn; Upper surface in this p type semiconductor layer forms transparency conducting layer; Carry out roughened for this layer at transparent layer with the autoxidation etching technique, make this transparency conducting layer have rough surface; And a plurality of electrodes of formation.
In addition, the present invention also provides a kind of light-emitting diode, comprising: a plurality of brilliant material layers of heap of stone, and these a plurality of brilliant material layers of heap of stone comprise resilient coating, n type semiconductor layer, luminescent layer and p type semiconductor layer in regular turn; With the transparency conducting layer that this p type semiconductor layer contacts, wherein this transparency conducting layer has roughened surface; And a plurality of electrodes.
Description of drawings
Fig. 1 illustrates the schematic diagram that forms a plurality of stacked crystal layer structures according to an embodiment of method for making of the present invention on substrate.
Fig. 2 illustrates the schematic diagram that forms transparency conducting layer according to an embodiment of method for making of the present invention on a plurality of epitaxial layers.
The embodiment that Fig. 3 illustrates according to method for making of the present invention carries out the schematic diagram that surface coarsening is handled to transparency conducting layer " directly ".
The embodiment that Fig. 4 illustrates according to method for making of the present invention finishes the schematic diagram that the surface coarsening of transparency conducting layer is handled.
The schematic diagram of the light-emitting diode that provides according to one embodiment of the invention is provided Fig. 5.
Fig. 6 illustrates the relation of the luminous efficiency of surperficial roughening treatment time and light-emitting diode.
Fig. 7 illustrates the generalized section without the transparency conducting layer of roughened.
Fig. 8 illustrates the generalized section of the transparency conducting layer of handling through the autoxidation etching technique.
[primary clustering symbol description]
1 light-emitting diode
11 substrates
12 resilient coatings
13 n type semiconductor layer
14 luminescent layers
15 p type semiconductor layer
16 transparency conducting layers
The I upper surface
The II rough surface
17,18 electrodes
Embodiment
Below describe the present invention in detail with embodiment, these embodiment are illustrative, but not in order to the restriction the present invention.
Method of the present invention is included in and forms a plurality of brilliant material layers of heap of stone on the substrate, and these a plurality of brilliant material layers of heap of stone can be n type and p type contact structure (p-n junction), comprises resilient coating, n type semiconductor layer, luminescent layer in regular turn, reaches the p type semiconductor layer.Then, form transparency conducting layer at the upper surface of this p type semiconductor layer, and " directly " with the autoxidation etching technique this transparency conducting layer is carried out roughened so that this transparency conducting layer has rough rough surface.In the present invention, mentioned " autoxidation etching technique " is defined as, do not need extra use shielding (mask) to be covered on this transparency conducting layer to form specific pattern, but see through the directly extensive etched mode of area, remove layer at transparent layer thickness molecular layer (monolayer) as thin as a wafer, and then reach the purpose of the material (for example metal oxide) of this transparency conducting layer of roughening itself; Wherein, this molecular layer is formed on layer at transparent layer by this transparency conducting layer itself through oxidation or other chemical reaction, and thickness can be micron (μ m) or nanometer (nm) size.At last, a plurality of electrodes are set, comprise with n type semiconductor layer electrodes in contact and with this transparency conducting layer electrodes in contact of part, and form the primary structure of this light-emitting diode.
With call in the following text " group III nitride compound " refer to comprise the compound that belongs to triels (for example aluminium (Al), gallium (Ga), indium (In)) in the nitrogen (N) and the periodic table of chemical element, with and aluminum indium nitride gallium (Al
xIn
yGa
1-x-yN, wherein 0≤x≤1,0≤y≤1,0≤x+y≤1) compound.
Please refer to Fig. 1 to Fig. 5, it illustrates the schematic flow sheet of making light-emitting diode according to one embodiment of the invention.With reference to Fig. 1, at first substrate 11 is inserted brilliant depositing system of heap of stone, wherein the upper surface of this substrate 11 can patterned (figure show).These substrate 11 materials are selected from sapphire (Al
2O
3), GaAs (GaAs), indium phosphide (InP), silicon (Si), carborundum (SiC), gallium nitride (GaN), zinc oxide (ZnO) or other material that is fit to.
Upper surface at this substrate 11 forms a plurality of layers of epitaxial structure of forming with group III nitride compound (for example gallium nitride, indium nitride, aluminium nitride) and/or oxygen compound (for example zinc oxide) with brilliant deposition of heap of stone (for example Metalorganic chemical vapor deposition (MOCVD) or sputter (sputter)), comprises resilient coating 12, n type semiconductor layer 13, luminescent layer 14 and p type semiconductor layer 15 in regular turn.This luminescent layer 14 can be multiple quantum trap, and (Multiple Quantum Well MQW) forms.According to design requirement, this multilayer epitaxial structure also can comprise other material layer, also can a plurality of groups of semiconductor layers or the more complicated structure applications of a plurality of active layers in this luminescent layer.
With reference to Fig. 2, at the upper surface formation transparency conducting layer 16 of this p type semiconductor layer 15, wherein this transparency conducting layer 16 has upper surface I.Selecting this transparency conducting layer 16 to possess high work function (high work function, Φ m (eV)) thin-film material by wide energy gap (high energy band, Eg (eV)) metal oxide or other suitable metal forms.
With the metal oxide is example, and this transparency conducting layer 16 is optional from the thin-film material of energy gap between 3.2 electron-volts to 4.9 electron-volts, comprising: gallium oxide (Ga
2O
3), aluminium oxide (Al
2O
3), tin indium oxide, tin oxide (SnO
2), indium oxide (In
2O
3), zinc oxide (ZnO), the zinc oxide (doped ZnO) that mixes.This transparency conducting layer 16 also can be selected from work function greater than 5.0 electron-volts material, comprising: nickel (Ni), gold (Au), palladium (Pd), platinum (Pt), ruthenium (Ru), iridium (Ir), chromium metallic film materials such as (Cr).
In one embodiment, this transparency conducting layer 16 can be made of zinc oxide, its can sputter-deposited at the upper surface of this p type semiconductor layer 15.This zinc oxide can be the zinc oxide (ZnO) of undoped or through the atom doped zinc oxide of boron (B doped, BZO), atom doped zinc oxide (the Ga doped of gallium, GZO), atom doped zinc oxide (the Al doped of aluminium, AZO), zinc oxide (the P doped of phosphorus atoms doping, ZnO:P), the atom doped zinc oxide of arsenic (As doped, ZnO:As).
Then,, the upper surface I of this transparency conducting layer 16 is carried out roughened with the autoxidation etching technique, shielding need not be set separately with reference to Fig. 3.This autoxidation etching technique can dry ecthing or the mode of wet etching carry out.
The mode of dry ecthing can be utilized for example plasma etching (plasma etching), laser-induced thermal etching (laser etching), ion beam milling (ion beam etching), sputter-etch (sputter etching), reactive ion etching (reactive ion etching) or inductively coupled plasma ion(ic) etching modes such as (inductively coupled plasma reactive ion etching).
Wet etching is to use etchant to have the characteristic of selective etch for transparent conductive material.In one embodiment, this etchant is an acid solution, is to be selected from sulfuric acid (H
2SO
4), phosphoric acid (H
3PO
4), nitric acid (HNO
3), nitrous acid (HNO
2), phosphorous acid (H
3PO
3), hydrochloric acid (HCl), acetic acid (CH
3COOH), carbonic acid (H
2CO
3), boric acid (H
2BO
3), formic acid (HCOOH), acid iodide (HIO
3), oxalic acid (H
2C2O
4), hydrofluoric acid (HF), hydrogen sulfide (H
2S), sulfurous acid (H
2SO
3), fluosulfonic acid (HSO
3F), any alkyl sulfonic acid (RSO
3F, R=C
nH
2n+1), ferric trichloride (FeCl
3) in one or more mixtures.
In another embodiment, this etchant also can be aqueous slkali, is to be selected from NaOH (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca (OH)
2), tetramethyl-ammonium hydroxide (TMAH), ammonium hydroxide (NH
4OH), sodium carbonate (Na
2CO
3), sodium acid carbonate (NaHCO
3), potash (K
2CO
3), barium hydroxide (Ba (OH)
2), hydrogen peroxide (H
2O
2) in one or more mixtures.
In one embodiment, this light-emitting diode 1 can be immersed in about 5 ℃ to about 200 ℃ ferric trichloride (FeCl that comprises
3) with the etchant of hydrochloric acid (HCl) mixed solution in carry out the autoxidation etching step of this transparency conducting layer 16 surperficial I, make the upper surface of this transparency conducting layer 16 form rough structure, that is, rough surface II as shown in Figure 4, therefore this rough surface II possesses arbitrary graphic pattern, and these arbitrary graphic patterns can be rule or irregular pattern.According to etching period, the rough surface II of this transparency conducting layer 16 can have roughness in various degree.After finishing surperficial autoxidation etching step, clean this assembly surface with organic solution.
Then, can handle with for example micro-photographing process, form through hole 16A with expose portion n type semiconductor layer 13 and at this transparency conducting layer 16, from this p type semiconductor layer 15 of through hole 16A expose portion to this assembly with reference to Fig. 5.Then, can utilize for example electron gun evaporation (electron-beam evaporation) or other metal deposition that is fit to, a plurality of electrodes 17,18 are set, it comprises with this n type semiconductor layer 13 electrodes in contact 18, reaches through through hole 16A and this p type semiconductor layer 15 and transparency conducting layer 16 electrodes in contact 17, forms light-emitting diode shown in Figure 51 thus.This light-emitting diode 1 comprises a plurality of brilliant material layers of heap of stone, comprise resilient coating 12, n type semiconductor layer 13, luminescent layer 14 in regular turn, reach p type semiconductor layer 15, contact and have the transparency conducting layer 16 of rough surface II and a plurality of electrode 17,18 with this p type semiconductor layer 15.Be worth mentioning, for promoting the heat radiation of this light-emitting diode 1, also removable this substrate 11 and a side setting of n type semiconductor layer 13 substrate with preferable thermal conductivity.
The test example
With ferric trichloride and hydrochloric acid mixed solution as etchant, under about 5-200 ℃ temperature conditions, directly transparency conducting layer 16 is carried out the surface roughening processing (that is, using shielding) of different etching periods, and prepare LED matrix according to aforesaid method, then carry out the luminous efficiency experiment measuring.
The result as shown in Figure 6, with the optical output power of the transparency conducting layer (being that etching period is 0) handled without surface roughening as benchmark 1.00, the optical output power of the transparency conducting layer of handling through surface roughening in various degree (being that etching period is about 15 to about 45 seconds) relatively.As shown in Figure 6, when etching period increases to about 30-35 second, the optical output power of assembly raises with etching period, this shows that carrying out surface roughening with autoxidation etching technique of the present invention handles, can cause the rough structure of this layer at transparent layer, and this structure increases in time and increases, and reaches the effect of the light total internal reflection that reduces assembly, and then reaches lifting light-emitting diode assembly light extraction efficiency.Yet etching period long (above 35 seconds) easily etches away most transparency conducting layer, makes electric current can't be dispersed evenly to whole assembly on the contrary, causes the luminous efficiency decay of LED.
In addition, shown in Fig. 7 profile (promptly, being equivalent to Fig. 3 A place amplifies), measurement is about 270 nanometers without the integral thickness of the transparency conducting layer 16 of roughened, the surface forms thickness molecular layer (monolayer) as thin as a wafer through oxidation or other chemical reaction, and this molecular layers thick is about micron (μ m) or nanometer (nm) size.Again, shown in Fig. 8 profile (promptly, being equivalent to Fig. 4 B place amplifies), after this transparency conducting layer 16 carries out the surface roughening processing with the autoxidation etching technique, the integral thickness of measuring this transparency conducting layer 16 is about 254 nanometers, and can reach about 67.5 nanometers through the formed thickness disparity drop of roughened, confirm that the autoxidation etching technique really can form rough structure in this layer at transparent layer, and then reach the effect of improving the light-emitting diode assembly light extraction efficiency.
To sum up state, according to preparation method of the present invention, directly the metal oxide materials to transparency conducting layer itself carries out surface roughening processing (that is not setting or use shielding separately), make its surface possess the rough surface of arbitrary graphic pattern, can reach the effect that promotes luminous efficiency.Again, according to preparation method of the present invention, then light shield need not be set separately, also need not define mask pattern separately, can reach and simplify fabrication steps, reduce manufacturing cost and shorten advantage such as manufacturing time.
Though content basis previous drawings of the present invention and preferred embodiment disclose as described above, it will be understood by a person skilled in the art that its content is not to be to limit category of the present invention.The replacement system of its enforcement and mode are advised by the front narration, and are easily considered the system and the mode of other replacement by those skilled in the art.Create according to the spirit of structure of the present invention and method any have be same as function of the present invention person as a result in fact, all do not break away from category of the present invention; Therefore, all these replace and revise, all be intended to drop on claims of the application and specification, with and the category of impartial system and method among.
Claims (15)
1. manufacturing method for LED comprises:
Form a plurality of brilliant material layers of heap of stone on substrate, these a plurality of brilliant material layers of heap of stone comprise resilient coating, n type semiconductor layer, luminescent layer and p type semiconductor layer in regular turn;
Upper surface in this p type semiconductor layer forms transparency conducting layer;
Carry out roughened for this transparency conducting layer with the autoxidation etching technique, make this transparency conducting layer have rough surface; With
Form a plurality of electrodes.
2. the method for claim 1, wherein these a plurality of brilliant material layers of heap of stone are by aluminum indium nitride gallium Al
xIn
yGa
1-x-yThe N compound is formed, wherein 0≤x≤1,0≤y≤1,0≤x+y≤1.
3. the method for claim 1, wherein this transparency conducting layer is selected from the zinc oxide of gallium oxide, aluminium oxide, tin indium oxide, tin oxide, indium oxide, unadulterated zinc oxide, doping.
4. the method for claim 1, wherein this transparency conducting layer is selected from the film of nickel, gold, palladium, platinum, ruthenium, iridium, chromium or their alloy.
5. the method for claim 1, wherein this autoxidation etching technique be with directly with dry ecthing or wet etching mode, remove the layer at transparent layer molecular layer.
6. method as claimed in claim 5, wherein this molecular layer is layer at transparent layer through oxidation or other chemical reaction and forms.
7. method as claimed in claim 5, wherein this dry ecthing comprises modes such as plasma etching, laser-induced thermal etching, ion beam milling, sputter-etch, reactive ion etching or inductively coupled plasma ion(ic) etching.
8. method as claimed in claim 5, wherein this wet etching is as etchant with acid solution or aqueous slkali.
9. method as claimed in claim 8, wherein this acid solution is selected from one or more combinations in sulfuric acid, phosphoric acid, nitric acid, nitrous acid, phosphorous acid, hydrochloric acid, acetic acid, carbonic acid, boric acid, formic acid, acid iodide, oxalic acid, iron chloride, hydrofluoric acid, hydrogen sulfide, sulfurous acid, fluosulfonic acid, alkyl sulfonic acid, the oxide etching agent.
10. method as claimed in claim 8, wherein this aqueous slkali is selected from one or more combinations in NaOH, potassium hydroxide, calcium hydroxide, tetramethyl-ammonium hydroxide, ammonium hydroxide, sodium carbonate, sodium acid carbonate, potash, the barium hydroxide.
11. the method for claim 1 wherein contacts with this p type semiconductor layer for the through hole that passes this transparency conducting layer one of in these a plurality of electrodes.
12. a light-emitting diode comprises:
A plurality of brilliant material layers of heap of stone, these a plurality of brilliant material layers of heap of stone comprise resilient coating, n type semiconductor layer, luminescent layer and p type semiconductor layer in regular turn, wherein these a plurality of brilliant material layers of heap of stone are formed with group III nitride compound;
The transparency conducting layer that contacts with this p type semiconductor layer, wherein this transparency conducting layer has the coarse surface that forms with the autoxidation etching technique; And
A plurality of electrodes.
13. method as claimed in claim 12, wherein this group III nitride compound is aluminum indium nitride gallium Al
xIn
yGa
1-x-yN compound, wherein 0≤x≤1,0≤y≤1,0≤x+y≤1.
14. light-emitting diode as claimed in claim 12, wherein this coarse surface has arbitrary graphic pattern.
15. light-emitting diode as claimed in claim 12 wherein contacts with this p type semiconductor layer for the through hole that passes this transparency conducting layer one of in these a plurality of electrodes.
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|---|---|---|---|
| CN2012100187998A CN103219433A (en) | 2012-01-20 | 2012-01-20 | Light emitting diode and manufacturing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100187998A CN103219433A (en) | 2012-01-20 | 2012-01-20 | Light emitting diode and manufacturing method thereof |
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Family
ID=48817051
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| CN2012100187998A Pending CN103219433A (en) | 2012-01-20 | 2012-01-20 | Light emitting diode and manufacturing method thereof |
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| CN103700746A (en) * | 2013-12-10 | 2014-04-02 | 西安交通大学 | Light-emitting semiconductor device |
| WO2020020341A1 (en) * | 2018-07-26 | 2020-01-30 | 京东方科技集团股份有限公司 | Light-emitting diode structure, fabrication method therefor, and display panel |
| WO2020192364A1 (en) * | 2019-03-22 | 2020-10-01 | 京东方科技集团股份有限公司 | Array substrate, preparation method therefor, and display device |
| CN111755576A (en) * | 2019-03-28 | 2020-10-09 | 中国科学院物理研究所 | Amorphous gallium oxide etching method and application in three-terminal device and array imaging system |
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Application publication date: 20130724 |