CN1219333C - Method for producing white light-emitting diode - Google Patents
Method for producing white light-emitting diode Download PDFInfo
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- CN1219333C CN1219333C CNB021285187A CN02128518A CN1219333C CN 1219333 C CN1219333 C CN 1219333C CN B021285187 A CNB021285187 A CN B021285187A CN 02128518 A CN02128518 A CN 02128518A CN 1219333 C CN1219333 C CN 1219333C
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Abstract
The present invention relates to a method for producing a white light-emitting diode. The method comprises the following producing steps: (1) selecting the material of a substrate to generate the required material of the epitaxial growth on the substrate as the next substrate; (2) passivating the surface of the material; (3) generating a nanometer dimensional quantum points as an induced layer on the substrate; (4) then, generating at least one layer of heterogeneity quantum point structure as an active layer of the light-emitting diode; (5) generating a layer of P-type material on the active layer; (6) plating a layer of electrodes. The white light-emitting diode produced by the method has the advantages of simple producing process, high repeatability, adjustable light-emitting waveband and adjustable color.
Description
Technical field
The present invention relates to semi-conducting material and device, be meant a kind of method of making white light emitting diode especially.
Background technology
Along with the fast development of optoelectronics research, the development of white light-emitting diodes becomes the focus that present world many countries is paid close attention to, and people generally acknowledge that generally light-emitting diode (LED) light source is continue incandescent lamp, the later third generation lighting source of fluorescent lamp.This novel illumination instrument each side index all is far superior to present product, has high cost performance.At first, secondly the power consumption of a light-emitting diode is that lifetime of LED is long far below traditional bulb, can reach more than 10 years.The characteristics that the white light-emitting diode volume is little, low in energy consumption, brightness is strong and heat is low also are suitable as automobile tail light, flight emergency warning lamp and runway lights etc. very much.White light-emitting diode can be widely used in office equipment demonstration, automotive lighting demonstration, general lighting and various military equipment.The U.S. " the laser world " once write articles and claims will account for more than 55% of illuminations market to this new product in 2025, and the electricity that the annual whole world uses this new light sources to save can reach 1,000 hundred million dollars.
Could a challenge so just have been proposed: how from the monochromatic light light-emitting diode, obtain white light? the method that present people make white light-emitting diodes mainly contains:
(1) a kind of method is that light-emitting diode with different colours mixes the generation white light.Just as TV produces shades of colour with red-hot red, green, blue look fluorescent material, also comprise white certainly.Appropriate single color LED combination also can produce white light, standard combination is the combination of red, green, blue look diode, and best of breed only gets final product with blue and two kinds of light-emitting diodes of tangerine look, and the color of emission can change according to the different capacity control that is added on each light-emitting diode chip for backlight unit.
(2) second method is that other can send the material of white light with the light-emitting diode de-energisation.A kind of device of being made up of gallium nitride can send blue light, is coated with the last layer phosphor in the inside of this device, and phosphor can produce white light after being subjected to the blue light irradiation, thereby has realized a white light emitter.Blue photons has higher energy, be enough to trigger phosphor emission white light, this monolithic white light emitting diode is with blue light-emitting diode deexcitation phosphor material, can send sodium yellow, yellow and blue stack one time-out of the eye-observation light that just is white in color, white light emitting diode has begun to use in traffic signals, automobile, instrument.But the white light color rendering that this method produces is good inadequately.
(3) the third method be with gallium nitride (GaN) thus the base ultraviolet light source excites three-color phosphor to form white light, principle is the same.
(4) researcher in Boston University's photon research center has proposed a kind of white light-emitting diodes recently, and it combines above-mentioned two kinds of methods.Their " photon recirculation " device is made up of two light-emitting diodes, and they are on same chip, and the light-emitting diode of being made by aluminium cigarette gallium phosphorus (AllnGaP) semiconductor compound is stacked on the gallium nitride light-emitting diode of the coloured light that turns blue.Blue light bump AllnGaP layer; Some blue photons release energy and produce bisque photon; Other photon is then by the AllnGaP alloy-layer.
But there are some problems in the white light emitting diode of these method mades at present.For example incandescent lamp bulb has very strong sodium yellow composition, gives a kind of warm sensation of people.But the white light that white fluorescent material, light-emitting diode send obviously has the blue light composition.Under the illumination of this white light emitting diode, all seem all not too natural, differ too big with the situation on daytime.This also has the problem of complex process the method for employing fluorescence excitation.
Summary of the invention
The purpose of this invention is to provide a kind of method of making white light emitting diode, it adopts easy feasible technological to make white light emitting diode, has integrated level and improves volume decline, and technology stability improves.
Another object of the present invention is to provide a kind of method of making white light emitting diode, the white light emitting diode of its made, glow color can be regulated by the size of adjusting component and quantum dot easily, and color can be adjusted as required easily.
A further object of the present invention is to provide a kind of method of making white light emitting diode, do not resemble in the additive method of present employing need be in the technology of back integrated other single color LED, or add and be coated with this technology of fluorescence.
In order to realize purpose of the present invention, the present invention adopts following method:
(1) select backing material, the epitaxial growth of gallium nitride sill is as next step substrate on this substrate;
(2) material surface is carried out passivation;
(3) on above-mentioned substrate, grow the gallium nitrate based quantum dot of one deck as inducing layer;
(4) one or more layers heterogeneous gallium nitrate based quantum-dot structure of regrowth on inducing layer, the gallium nitrate based quantum-dot structure of list of being grown or heterogeneous multi-layer is as the active layer of light-emitting diode;
(5) regrowth one deck P-type material on active layer;
(6) plating one deck electrode on P-type material.
Wherein the said substrate of step (1) comprises foreign substrate and homo-substrate; Comprise and adopt the homogeneity gallium nitride single crystal, perhaps heterogeneous sapphire, silicon single crystal, spinelle, carborundum, aluminium nitride, zinc oxide, developing zinc oxide compound substrate on growing aluminum nitride compound substrate, the silicon on grow on the silicon aluminium oxide compound substrate, the silicon.
Wherein the said passivation of step (2) comprises multiple passivating method, the gas passivation, or adopt hydrogen, oxygen carries out passivation to the surface; Or liquid, solid passivation, or adopt sulfide, oxide.
The gallium nitrate based quantum-dot structure of the said growth heterogeneous multi-layer of step (4) wherein, each layer thickness be 1 nanometer to 500 nanometers, be different materials between the different layers or be same material that its material is meant III group-III nitride sill.
Wherein the said P-type material of step (5) is the semi-conducting material that the hole can be provided.
Wherein step (6) said on P-type material plating one deck electrode, this electrode is combination electrode or single-layer electrodes, electrode material is aluminium, platinum, gold, nickel metal material.
Description of drawings
The present invention is further described content of the present invention in order better to illustrate below in conjunction with drawings and Examples, wherein:
Fig. 1 is the sectional view of nitride multilayer gallium based quantum dot white light emitting diode of the present invention.
Embodiment
A kind of method of making white light emitting diode is characterized in that, this method comprises and is prepared as follows step:
(1) select backing material, the epitaxial growth of gallium nitride sill is as next step substrate on this substrate; Said substrate can be that foreign substrate also can be a homo-substrate; As: growth III group-III nitride just can adopt the homogeneity gallium nitride single crystal, perhaps heterogeneous sapphire, silicon single crystal, spinelle, carborundum, aluminium nitride, zinc oxide, on the silicon on growth aluminium oxide compound substrate, the silicon on growing aluminum nitride compound substrate, the silicon developing zinc oxide compound substrate and or the like various compound substrate.
(2) material surface is carried out passivation; Said passivation can be multiple passivating method, and as the gas passivation, as adopting hydrogen, oxygen carries out passivation to the surface; Also can be liquid, solid passivation, as various sulfide, oxide or the like; As long as can effectively fill the dangling bonds of substrate surface, the transition potential barrier that improves surface atom gets final product.
(3) on above-mentioned substrate the quantum dot of growth one deck nano-scale as inducing layer.
(4) and then one or more layers hetero quntum point structure of growing, the single/multiple layer hetero quntum point structure of being grown is as the active layer of light-emitting diode; Said growth multiple layer hetero quntum point structure, each layer thickness be 1 nanometer to 500 nanometers, can be different materials between the different layers, also can be same material between the different layers, its material mainly is meant III nitride base and II-VI family sill.
(5) regrowth one deck P-type material on active layer; Said P-type material can be the various semi-conducting materials that the hole can be provided.
(6) plating one deck electrode; Said plating one deck electrode, this electrode can be that combination electrode also can be a single-layer electrodes, and electrode material can be the metal material that aluminium, platinum, gold, nickel or the like are suitable for.
Said " semi-conducting material " mainly comprises compound semiconductors such as III group-III nitride and II-VI family.
Said " heterogeneous " refers to two kinds of semi-conducting materials that composition is different.Both the most essential differences are energy gap differences, promptly in two kinds of semi-conducting materials, an energy difference are arranged between the energy at the bottom of the conduction band or between the energy between the top of valence band.
Said " passivation " implication is as follows: can be multiple passivating method.Can be the gas passivation, as adopting hydrogen, oxygen carries out passivation to the surface.Also can be liquid, solid passivation, as various sulfide, oxide or the like.As long as can effectively fill the dangling bonds of substrate surface, the transition potential barrier that improves surface atom gets final product.
Said plural layers are index layer film structures, and every layer film is made of different materials.
Principle of the present invention is: the III group-III nitride has very big piezoelectric constant, for example: the e of InN
31=-0.37C/m
2, GaN is-0.22C/m
2And 0.49C/m
2, that AlN is 0.48C/m
2And 0.6C/m
2So when the III-N compound is in strain regime, can produce big piezoelectric effect.In GaN, incorporate the lattice constant that Al and In can obviously change alloy into, so in the heterojunction of the binary of III group-III nitride or ternary, quantum well, quantum-dot structure, have very big piezoelectric field.Except piezoelectric polarization, on [0001] direction, also there is big spontaneous polarization, if a kind of material has only the polaxis of a list in balance, it will polarize so.[0001] direction of six side's gallium nitride is exactly this situation.Therefore six side GaN exist on [0001] direction by piezoelectric field and the caused very big internal electric field of spontaneous polarization electric field, and its value of bibliographical information can reach the MV/cm magnitude.At this moment the band structure of the GaN/InGaN quantum dot of (0001) face can be subjected to the very big influence of internal electric field, this internal electric field will skew being with, make effective band edge descend, so exist the quantum dot transition energy of internal electric field to be lower than the transition energy of the quantum dot that does not have internal electric field, so-called quantum limit Stark effect that Here it is (Quantum Confined Stark Effect (QCSE)).The quantum limit Stark effect will cause the red shift of emission peak peak position.Multi-layer quantum point is because every layer of size difference, wherein the internal electric field of Cun Zaiing varies in size, so the amount of glow peak red shift is just different, thereby the size of component that can be by adjusting material and quantum dot forms the light of indigo plant, color such as green, yellow, red, thereby each layer quantum dot issued light superposes and synthesizes white light.
Compare with technology in the past, this invention has following meaning:
1) owing to adopt multi-layer quantum point as active layer, the luminescent layer of each wave band is concentrated on the chip, needn't adopt multiple monochrome photodiode to be combined into array, makes integrated level improve volume and descends, and technology stability improves.2) suitable material and the thickness of selection just can make the photon mixing of passing through produce white light.Glow color can be regulated by the size of adjusting component and quantum dot easily, and color can be adjusted as required easily.3) all adopt ripe semiconductor technology, thereby technical stability is good, cost is low, need not add any new technology and process equipment and can finish, and needn't adopt once more the method for fluorescence excitation to produce white light, thereby avoid complicated technology.
Embodiment one: nitrogen indium gallium (InGaN) multi-layer quantum point white light emitting diode
See also shown in Figure 1, according to the sectional view of the InGaN multi-layer quantum point white light emitting diode of first embodiment of the invention.The preparation of this structure comprises following process:
1. consult Fig. 1, adopt (0001) surface sapphire (C-Al
2O
3) 1 make substrate.
2. the resilient coating 2 of epitaxial growth one deck gallium nitride on (0001) surface sapphire substrate, resilient coating 10-50nm is thick, and growth temperature is 450-600 ℃.
On resilient coating the growth certain thickness n type gallium nitride 3, growth temperature 1000-1100 ℃, thickness is the 0.5-4 micron.
4. gallium nitride film is carried out passivation.
5. growing low temperature gallium nitride quantum dot 4 on gallium nitride template is as adjusting layer.
6. on the gallium nitride quantum dot, cover one or more layers InGaN quantum dot 5, as the active layer of device.The structure of concrete growth conditions and multilayer film is decided on designed structure.
7. the P type layer 6 of 0.5 to 3 micron of growth on active layer.
8. growth one deck electrode layer 7 on P type layer.
Substrate in the step 1 removes (0001) surface sapphire (C-Al
2O
3) outside, also can adopt the sapphire of any one face to do substrate, perhaps gallium nitride (GaN) monocrystalline, silicon single crystal (Si), spinelle (MgAl
2O
4), carborundum (SiC), aluminium nitride (AlN), zinc oxide (ZnO), growth aluminium oxide compound substrate (Al on the silicon
2O
3/ Si), various compound substrate of developing zinc oxide compound substrate (ZnO/Si) and AlN/SiC or the like on growing aluminum nitride compound substrate (AlN/Si), the silicon on the silicon.In a word, as long as can make the III group-III nitride of extension on this substrate have preferable quality to can be used as the template of GaN quantum dot.Though extension can obtain same effect on multiple substrate, we think that to do substrate with (0001) surface sapphire at present better, and this substrate is compared with other substrates has cheapness, the advantage that is easy to obtain.
The epitaxial growth method of each material employing MOCVD method is present best mode among the step 2-4.
Passivation in the step 4 can be various effective passivating methods.Comprise various oxidants, sulfide, hydride.As long as can effectively fill the dangling bonds of gallium nitride surface, increase the diffusion into the surface potential barrier and get final product.
Quantum dot is a multilayer in the step 6, and the number of plies is not limit, and each layer thickness is that 1 nanometer is to 500 nanometers.Can be different materials between the different layers, for example A, the B that is indicated among Fig. 1, C represent different dissimilar materials layers respectively; Also can be same material between the different layers.For example the A layer is identical with the C layer different with the B layer again, thereby constitutes a double-heterostructure.
Claims (6)
1. a method of making white light emitting diode is characterized in that, this method comprises and is prepared as follows step:
(1) select backing material, the epitaxial growth of gallium nitride sill is as next step substrate on this substrate;
(2) material surface is carried out passivation;
(3) on above-mentioned substrate, grow the gallium nitrate based quantum dot of one deck as inducing layer;
(4) one or more layers heterogeneous gallium nitrate based quantum-dot structure of regrowth on inducing layer, the gallium nitrate based quantum-dot structure of list of being grown or heterogeneous multi-layer is as the active layer of light-emitting diode;
(5) regrowth one deck P-type material on active layer;
(6) plating one deck electrode on P-type material.
2. a kind of method of making white light emitting diode according to claim 1 is characterized in that, wherein the said substrate of step (1) comprises foreign substrate and homo-substrate; Comprise and adopt the homogeneity gallium nitride single crystal, perhaps heterogeneous sapphire, silicon single crystal, spinelle, carborundum, aluminium nitride, zinc oxide, developing zinc oxide compound substrate on growing aluminum nitride compound substrate, the silicon on grow on the silicon aluminium oxide compound substrate, the silicon.
3. a kind of method of making white light emitting diode according to claim 1 is characterized in that, wherein the said passivation of step (2) comprises multiple passivating method, the gas passivation, or adopt hydrogen, oxygen carries out passivation to the surface; Or liquid, solid passivation, or adopt sulfide, oxide.
4. a kind of method of making white light emitting diode according to claim 1, it is characterized in that, the gallium nitrate based quantum-dot structure of the said growth heterogeneous multi-layer of step (4) wherein, each layer thickness is that 1 nanometer is to 500 nanometers, it between the different layers different materials or for same material, its material is meant III group-III nitride sill.
5. a kind of method of making white light emitting diode according to claim 1 is characterized in that, wherein the said P-type material of step (5) is the semi-conducting material that the hole can be provided.
6. a kind of method of making white light emitting diode according to claim 1, it is characterized in that, wherein step (6) said on P-type material plating one deck electrode, this electrode is combination electrode or single-layer electrodes, electrode material is aluminium, platinum, gold, nickel metal material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021285187A CN1219333C (en) | 2002-08-09 | 2002-08-09 | Method for producing white light-emitting diode |
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|---|---|---|---|
| CNB021285187A CN1219333C (en) | 2002-08-09 | 2002-08-09 | Method for producing white light-emitting diode |
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|---|---|
| CN1474464A CN1474464A (en) | 2004-02-11 |
| CN1219333C true CN1219333C (en) | 2005-09-14 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1595670B (en) * | 2004-06-25 | 2011-12-28 | 清华大学 | Quanta dot active region structure of broad spectrum white light LED and epitaxial growth method thereof |
| CN100373534C (en) * | 2004-07-20 | 2008-03-05 | 中国科学院半导体研究所 | Method for manufacturing semiconductor nano structure on cleavage surface |
| US8941299B2 (en) * | 2006-05-21 | 2015-01-27 | Massachusetts Institute Of Technology | Light emitting device including semiconductor nanocrystals |
| GB201109065D0 (en) * | 2011-05-31 | 2011-07-13 | Nanoco Technologies Ltd | Semiconductor nanoparticle-containing materials and light emitting devices incorporating the same |
| CN102231422A (en) * | 2011-06-16 | 2011-11-02 | 清华大学 | Fluorescent-powder-free single-chip GaN (gallium nitride)-based LED (light-emitting diode) and manufacturing method thereof |
| CN106601880B (en) * | 2016-11-21 | 2019-06-11 | 华灿光电（浙江）有限公司 | Epitaxial wafer of gallium nitride-based light-emitting diode and preparation method thereof |
| CN116093223B (en) * | 2023-03-07 | 2023-06-16 | 江西兆驰半导体有限公司 | Light-emitting diode epitaxial wafer, preparation method thereof and light-emitting diode |
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