CN102270718B - Nitride light emitting diode (LED) structure and preparation method thereof - Google Patents
Nitride light emitting diode (LED) structure and preparation method thereof Download PDFInfo
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- CN102270718B CN102270718B CN 201110209405 CN201110209405A CN102270718B CN 102270718 B CN102270718 B CN 102270718B CN 201110209405 CN201110209405 CN 201110209405 CN 201110209405 A CN201110209405 A CN 201110209405A CN 102270718 B CN102270718 B CN 102270718B
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Abstract
The invention discloses a nitride light emitting diode (LED) structure, which comprises a substrate, a low-temperature nucleation layer and an undoped nitride layer, wherein the low-temperature nucleation layer and the undoped nitride layer grow on the substrate; a three-dimensional growth layer grows on the low-temperature nucleation layer; an AlxIn(1-x)N material layer is arranged between the three-dimensional growth layer and the undoped nitride layer and provided with a rough surface; the refractive index of the AlxIn(1-x)N material layer is different from that of the undoped nitride layer; and the x is more than 0 and less than 1. The invention also provides a preparation method of the nitride LED structure. The nitride LED structure provided by the invention changes the transmission direction of light rays due to a scattering effect, expands the critical angle of emergent light, and improves the light extraction efficiency and the external quantum efficiency. The preparation method provided by the invention can be compatible with the ordinary LED epitaxial growth process and is completed in a reaction chamber at one time, and extra machining or processing technologies are not needed.
Description
Technical field
The present invention relates to the LED preparing technical field, relate in particular to a kind of nitride LED structure and preparation method thereof.
Background technology
Light-emitting diode (LED, Light Emitting Diode) is a kind of semiconductor solid luminescence device, and it utilizes semiconductor PN as luminescent material, can directly electricity be converted to light.After the two ends of semiconductor PN add forward voltage, inject the minority carrier of PN junction and majority carrier and occur compoundly, emit superfluous energy and cause photo emissions, directly send the light that color is red, orange, yellow, green, blue, blue, purple.
Along with the exploitation that the high-brightness LED take nitride as the basis is used, new generation of green environment protection solid lighting source-nitride LED has become the focus that people pay close attention to.Having wide direct band gap, strong chemical bond, the premium properties such as high temperature resistant, anticorrosive take GaN, InGaN and AlGaN alloy as main III hi-nitride semiconductor material, is the ideal material of making short wavelength's high brightness luminescent device.
Because transversary is generally adopted in the manufacturing of LED device, build is that two sides, the cuboid left and right sides is parallel to each other, although the wide part that active area sends is from the top outgoing of p type island region, but, because the refractive index difference of semi-conducting material and air is larger, when causing LED light to be transmitted into the little air of refractive index from the large chip of refractive index, full emission can occur at the interface of semiconductor and air, undressed semiconductor LED body structure surface only has seldom a part of light to escape out from chip internal, thereby causes the light extraction efficiency of chip very low.Because the light extraction efficiency of chip is the principal element that determines the luminous efficiency of semiconductor lighting chip, therefore, promotes the luminous efficiency of nitride LED and the taking-up efficient of increase light and play a part very crucial to the external quantum efficiency that improves device.
In order to improve external quantum efficiency, people are attempting to attempt technically the various methods that can improve the chip light-emitting rate, such as patterned substrate technology (Patterned sapphire substrate), at smooth substrate surface, method by etching produces projection or the depression of regular how much shapes of nanometer or micro-meter scale, then carries out epitaxial growth LED structure at coarse like this substrate surface.The light that sends from LED structure active area is being mapped to epitaxial loayer and sapphire at the interface the time, and coarse interface can produce scattering process to light, has changed the Propagation of light rays direction, has expanded the critical angle of light outgoing, has improved and has got optical efficiency and external quantum efficiency.
Yet, adopt the method for mask and etching to form regular projection or sunk structure at substrate, this additional making technology can significantly improve production cost.In addition, for the epitaxy technique of substrate, carry out extension on the basis of carrying out surface coarsening technique, at first to coarse substrate figure be filled up, could epitaxial film is long flat, the extension time increases by 1～2 hour, not only reduce production efficiency, and increased raw-material consumption.
Summary of the invention
The object of the present invention is to provide a kind of nitride LED structure and preparation method thereof, form rough surface and the high problem of production cost that the photoetching process that adopts is brought to solve at substrate.
For addressing the above problem, the present invention proposes a kind of nitride LED structure, this nitride LED structure comprises substrate and at low temperature nucleating layer and the non-doped nitride layer of described Grown, growing three-dimensional grown layer on described low temperature nucleating layer is provided with an Al between described three dimensional growth layer and described non-doped nitride layer
xIn
1-xThe N material layer, described Al
xIn
1-xThe N material layer has rough surface, described Al
xIn
1-xThe refractive index of N material layer is different from the refractive index of described non-doped nitride layer, wherein, and 0＜x＜1.
Optionally, described Al
xIn
1-xThe lattice of N material layer and described three dimensional growth layer mates mutually.
Optionally, described nitride LED structure also is included in N-type nitride layer, multiple quantum well active layer, the P type nitride layer that forms successively on the described non-doped nitride layer, described Al
xIn
1-xThe energy gap of N material layer is greater than the energy gap of the quantum well of multiple quantum well active layer.
Optionally, in nitride LED structure, described Al
xIn
1-xThe rough surface that N material layer and described three dimensional growth layer have mutual coupling.
Optionally, in nitride LED structure, the rough surface of described three dimensional growth layer is island structure.
Optionally, in nitride LED structure, described Al
xIn
1-xRefractive index and the lattice parameter of N material layer pass through Al
xIn
1-xThe composition regulation of aluminium among the N.
Simultaneously, for addressing the above problem, the present invention also proposes a kind of preparation method of nitride LED structure, and the method comprises the steps: to provide substrate; On described substrate, form successively low temperature nucleating layer, three dimensional growth layer, Al
xIn
1-xThe nitride layer of N material layer, non-doping; Wherein, described Al
xIn
1-xThe N material layer has rough surface, and described Al
xIn
1-xThe refractive index of N material layer is different from the refractive index of described non-doped nitride layer.
Optionally, in the preparation method of nitride LED structure, described Al
xIn
1-xThe lattice of N material layer and described three dimensional growth layer mates mutually.
Optionally, on the nitride layer of described non-doping, form successively N-type nitride layer, multiple quantum well active layer, P type nitride layer, described Al
xIn
1-xThe energy gap of N material layer is greater than the energy gap of the quantum well of multiple quantum well active layer.
Optionally, in the preparation method of nitride LED structure, described Al
xIn
1-xThe N material layer has the rough surface that is complementary with described three dimensional growth layer.
Optionally, in the preparation method of nitride LED structure, the rough surface of described three dimensional growth layer is island structure.
Optionally, in the preparation method of nitride LED structure, method by metal organic chemical vapor deposition forms described low temperature nucleating layer at described substrate, and by the lifting technique temperature described low temperature nucleating layer is carried out the high temperature anneal, make described low temperature nucleating layer surface form bulge-structure.
Optionally, in the preparation method of nitride LED structure, the technological temperature that forms described low temperature nucleating layer is 500 ℃～700 ℃.
Optionally, in the preparation method of nitride LED structure, the lifting technique temperature until temperature value greater than 900 ℃.
Optionally, after the low temperature nucleating layer is carried out the high temperature anneal, pass into metal organic source and nitrogenous source described bulge-structure is carried out three dimensional growth.
Optionally, in the preparation method of nitride LED structure, described Al
xIn
1-xRefractive index and the lattice parameter of N material layer pass through Al
xIn
1-xThe composition regulation of aluminium among the N.
Optionally, in the preparation method of nitride LED structure, the method by metal organic chemical vapor deposition forms described Al
xIn
1-xThe N material layer, lifting technique temperature, Al
xIn
1-xThe component of aluminium increases among the N; Reduce technological temperature, Al
xIn
1-xThe component of aluminium reduces among the N.
Compared with prior art, nitride LED structure provided by the invention utilizes the Al with rough surface that arranges between described three dimensional growth layer and described non-doped nitride
xIn
1-xThe N material layer makes light be mapped to Al
xIn
1-xDuring the interface of the nitride layer of N material layer and non-doping, coarse interface can produce scattering process to light, has changed the Propagation of light rays direction, has expanded the critical angle of light outgoing, has improved and has got optical efficiency and outer quantum effect.
Compared with prior art, the preparation method of nitride LED structure provided by the invention is by forming successively low temperature nucleating layer, three dimensional growth layer, Al on substrate
xIn
1-xThe nitride layer of N material layer, non-doping, and make Al
xIn
1-xThe N material layer has coarse surface to satisfy certain light extraction efficiency, preparation method provided by the invention can be compatible with the LED epitaxial growth technology of common employing, in reative cell, once finish, and do not need to take other processing or making technology, solved at substrate and formed rough surface and problem that production cost that the photoetching process that adopts is brought improves.
Further, described Al
xIn
1-xThe energy gap of N material layer is greater than the energy gap of the quantum well of multiple quantum well active layer, so that the light that quantum well is sent can be by Al
xIn
1-xThe N material layer absorbs.
Description of drawings
The profile of the nitride LED structure that Fig. 1 provides for the embodiment of the invention;
The nitride LED preparation method flow chart of steps that Fig. 2 provides for the embodiment of the invention;
The cross-sectional view of device corresponding to each step among the preparation method of the nitride LED that Fig. 3 A to Fig. 3 C provides for the embodiment of the invention.
Embodiment
Nitride LED structure that the present invention is proposed below in conjunction with the drawings and specific embodiments and preparation method thereof is described in further detail.According to the following describes and claims, advantages and features of the invention will be clearer.It should be noted that accompanying drawing all adopts very the form of simplifying and all uses non-accurately ratio, only be used for convenient, the purpose of the aid illustration embodiment of the invention lucidly.
Core concept of the present invention is, a kind of nitride LED structure is provided, and utilizes the Al with rough surface that arranges between described three dimensional growth layer and described non-doped nitride
xIn
1-xThe N material layer makes light be mapped to Al
xIn
1-xDuring the interface of the nitride layer of N material layer and non-doping, coarse interface can produce scattering process to light, has changed the Propagation of light rays direction, has expanded the critical angle of light outgoing, has improved and has got optical efficiency and outer quantum effect; Simultaneously, also provide a kind of preparation method of nitride LED structure, by on substrate, forming successively low temperature nucleating layer, three dimensional growth layer, Al
xIn
1-xThe nitride layer of N material layer, non-doping, and make Al
xIn
1-xThe N material layer has coarse surface to satisfy certain light extraction efficiency, preparation method provided by the invention can be compatible with the LED epitaxial growth technology of common employing, in reative cell, once finish, and do not need to take other processing or making technology, solved at substrate and formed rough surface and problem that production cost that the photoetching process that adopts is brought improves.
Please refer to Fig. 1, the profile of the nitride LED structure that Fig. 1 provides for the embodiment of the invention, as shown in Figure 2, the nitride LED structure that the embodiment of the invention provides comprises substrate 101 and low temperature nucleating layer 102 and the non-doped nitride layer 104 of growing at described substrate 101, growing three-dimensional grown layer 108 on described low temperature nucleating layer is provided with an Al between described three dimensional growth layer 108 and described non-doped nitride layer 104
xIn
1-x N material layer 103, described Al
xIn
1-x N material layer 103 has rough surface, described Al
xIn
1-xThe refractive index of N material layer 103 is different from the refractive index of described non-doped nitride layer 104, wherein, and 0＜x＜1.
Further, described nitride LED structure also is included in N-type nitride layer 105, multiple quantum well active layer 106, the P type nitride layer 107 that forms successively on the described non-doped nitride layer 104, described Al
xIn
1-xThe energy gap of N material layer 103 is greater than the energy gap of the quantum well of multiple quantum well active layer 106, so that the light that multiple quantum well active layer 106 is sent can be by Al
xIn
1-x N material layer 103 absorbs.
Further, in nitride LED structure, described Al
xIn
1-xThe rough surface that N material layer 103 and described three dimensional growth layer 108 have mutual coupling, in the present embodiment, described rough surface is island structure, will be understood by those skilled in the art that, described rough surface not only is island structure, can also be other irregular structure.In the present embodiment, the material of described three dimensional growth layer 108 is gallium nitride.
Particularly, described Al
xIn
1-xThe refractive index of N material layer 103 and lattice parameter be by the composition regulation of Aluminum in Alloy, the rising growth temperature, and the component of Aluminum in Alloy increases, and reduces growth temperature, and the component of Aluminum in Alloy reduces.In the present embodiment, described Al
xIn
1-xIn the N material layer 103, the component of Al is preferably 83%, at this moment, and Al
xIn
1-xThe lattice of N material and the Lattice Matching of gallium nitride are best.
The nitride LED preparation method flow chart of steps that Fig. 2 provides for the embodiment of the invention.With reference to Fig. 2, the preparation method of nitride LED structure comprises the steps:
S21, provide substrate;
S22, on described substrate, form successively low temperature nucleating layer, three dimensional growth layer, Al
xIn
1-xThe nitride layer of N material layer, non-doping; Wherein, described Al
xIn
1-xThe N material layer has rough surface, described Al
xIn
1-xThe refractive index of N material layer is different from the refractive index of described non-doped nitride layer.
Below in conjunction with generalized section the method for preparing nitride LED structure of the present invention is described in more detail, the preferred embodiments of the present invention have wherein been represented, should be appreciated that those skilled in the art can revise the present invention described here, and still realize advantageous effects of the present invention.
Referring to Fig. 3 A, substrate 101 is provided, what adopt in the present embodiment is Sapphire Substrate, method by metal organic chemical vapor deposition forms described low temperature nucleating layer 102 at described substrate 101, in the present embodiment, the thickness range of the low temperature nucleating layer 102 of growth is 5 nanometers～100 nanometers, and the temperature of the low temperature nucleating layer 102 of growth is 500 ℃～700 ℃.Then, by the lifting technique temperature described low temperature nucleating layer 102 is carried out the high temperature anneal, in the present embodiment, technological temperature is increased to more than 900 ℃, low temperature nucleating layer 102 is being carried out in the high-temperature annealing process, the process of solid-state phase changes and atom desorption can occur, and some gallium atoms and nitrogen-atoms can break away from the surface of substrate 101, thereby make described low temperature nucleating layer 102 surfaces form bulge-structure.
Referring to Fig. 3 B, then, under the hot conditions of reative cell, pass into metal organic source and nitrogenous source, atomic molar ratio by control gallium atom and nitrogen-atoms carries out bulge-structure is carried out three dimensional growth, forms three dimensional growth layer 108, and the rough surface of described three dimensional growth layer 108 is island structure.
Referring to Fig. 3 C, coarse three dimensional growth layer 108 surface forming utilize Organometallic Chemistry gas phase process deposit one Al
xIn
1-x N material layer 103, described Al
xIn
1-x N material layer 103 mates mutually with the lattice of described three dimensional growth layer 108, with the problem that the epitaxial film of avoiding causing owing to plane stress ftractures, described Al
xIn
1-xThe refractive index of N material layer 103 is different from the refractive index of described non-doped nitride layer 104, is mapped to Al to guarantee light
xIn
1-xDuring the interface of N material layer 103 and described non-doped nitride layer 104, can improve light extraction efficiency.Described Al
xIn
1-xThe refractive index of N material layer 103 and lattice parameter be by the composition regulation of Aluminum in Alloy, the rising growth temperature, and the component of Aluminum in Alloy increases, and reduces growth temperature, and the component of Aluminum in Alloy reduces.Wherein, Al
xIn
1-xThe thickness of N material layer 103 is controlled by changing growth time or growth rate, under the constant condition of growth rate, increases growth time material thickness thickening, reduces growth time, the thickness attenuation of material; Under the constant condition of growth time, increase growth rate material thickness thickening; Reduce the attenuation of growth rate material thickness.In the present embodiment, described Al
xIn
1-xThe thickness of N material layer 103 is 0.01 micron～1 micron.
Among the nitride LED preparation method that the embodiment of the invention provides, crucial step is exactly the Al with rough surface that forms
xIn
1-x N material layer 103 is by forming Al
xIn
1-xThe rough surface of N material layer 103 is so that light is mapped to Al
xIn
1-xDuring the interface place of N material layer 103 and described non-doped nitride layer 104, because the scattering process of light occurs both refractive index differences, can greatly improve light extraction efficiency.
At last, with reference to figure 1, at shaggy Al
xIn
1-xCarry out the growth of non-doped nitride layer 104 on the N material layer 103, the atomic molar ratio by growth regulation temperature and gallium atom and nitrogen-atoms makes coarse nitride surface smooth gradually, with the basal layer as nitride LED structure.Afterwards, contain Al in inside
xIn
1-xGrow successively on the nitride film of N material layer 103 N-type nitride layer 105, multiple quantum well active layer 106, P type nitride layer 107.
Preparation method provided by the invention can be compatible with the LED epitaxial growth technology of common employing, in reative cell, once finish, and do not need to take other processing or making technology, solved at substrate and formed rough surface and problem that production cost that the photoetching process that adopts is brought improves.
Obviously, those skilled in the art can carry out various changes and modification to invention and not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (16)
1. nitride LED structure, comprise substrate and at low temperature nucleating layer and the non-doped nitride layer of described Grown, described low temperature nucleating layer surface forms bulge-structure, it is characterized in that, bulge-structure is grown, form coarse three dimensional growth layer surface, growing three-dimensional grown layer on described low temperature nucleating layer is provided with an Al between described three dimensional growth layer and described non-doped nitride layer
xIn
1-xThe N material layer, described Al
xIn
1-xThe N material layer has the rough surface that is complementary with described three dimensional growth layer, described Al
xIn
1-xThe refractive index of N material layer is different from the refractive index of described non-doped nitride layer, wherein, and 0＜x＜1.
2. nitride LED structure as claimed in claim 1 is characterized in that, described Al
xIn
1-xThe lattice of N material layer and described three dimensional growth layer mates mutually.
3. nitride LED structure as claimed in claim 1 is characterized in that, described nitride LED structure also is included in N-type nitride layer, multiple quantum well active layer, the P type nitride layer that forms successively on the described non-doped nitride layer, described Al
xIn
1-xThe energy gap of N material layer is greater than the energy gap of the quantum well of multiple quantum well active layer.
4. nitride LED structure as claimed in claim 1 is characterized in that, the rough surface of described three dimensional growth layer is island structure.
5. nitride LED structure as claimed in claim 1 is characterized in that, described Al
xIn
1-xRefractive index and the lattice parameter of N material layer pass through Al
xIn
1-xThe composition regulation of aluminium among the N.
6. the preparation method of a nitride LED structure is characterized in that, comprises the steps:
Substrate is provided;
On described substrate, form successively low temperature nucleating layer, three dimensional growth layer, Al
xIn
1-xThe nitride layer of N material layer, non-doping, described low temperature nucleating layer surface forms bulge-structure, and bulge-structure is grown, and forms coarse three dimensional growth layer surface;
Wherein, described Al
xIn
1-xThe N material layer has the rough surface that is complementary with described three dimensional growth layer, described Al
xIn
1-xThe refractive index of N material layer is different from the refractive index of described non-doped nitride layer, wherein, and 0＜x＜1.
7. the preparation method of nitride LED structure as claimed in claim 6 is characterized in that, described Al
xIn
1-xThe lattice of N material layer and described three dimensional growth layer mates mutually.
8. the preparation method of nitride LED structure as claimed in claim 6 is characterized in that, also comprises: form successively N-type nitride layer, multiple quantum well active layer, P type nitride layer on the nitride layer of described non-doping, described Al
xIn
1-xThe energy gap of N material layer is greater than the energy gap of the quantum well of multiple quantum well active layer.
9. the preparation method of nitride LED structure as claimed in claim 6 is characterized in that, described Al
xIn
1-xThe N material layer has the rough surface that is complementary with described three dimensional growth layer.
10. the preparation method of nitride LED structure as claimed in claim 9 is characterized in that, the rough surface of described three dimensional growth layer is island structure.
11. the preparation method of nitride LED structure as claimed in claim 9, it is characterized in that, method by metal organic chemical vapor deposition forms described low temperature nucleating layer at described substrate, and by the lifting technique temperature described low temperature nucleating layer is carried out the high temperature anneal, make described low temperature nucleating layer surface form bulge-structure.
12. the preparation method of nitride LED structure as claimed in claim 11 is characterized in that, the technological temperature that forms described low temperature nucleating layer is 500 ℃～700 ℃.
13. the preparation method of nitride LED structure as claimed in claim 12 is characterized in that, the lifting technique temperature until temperature value greater than 900 ℃.
14. the preparation method of nitride LED structure as claimed in claim 11 is characterized in that, after the low temperature nucleating layer is carried out the high temperature anneal, passes into metal organic source and nitrogenous source described bulge-structure is carried out three dimensional growth.
15. the preparation method of nitride LED structure as claimed in claim 6 is characterized in that, described Al
xIn
1-xRefractive index and the lattice parameter of N material layer pass through Al
xIn
1-xThe composition regulation of aluminium among the N.
16. the preparation method of nitride LED structure as claimed in claim 15 is characterized in that, the method by metal organic chemical vapor deposition forms described Al
xIn
1-xThe N material layer, lifting technique temperature, Al
xIn
1-xThe component of aluminium increases among the N; Reduce technological temperature, Al
xIn
1-xThe component of aluminium reduces among the N.
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| CN104733576B (en) * | 2015-02-28 | 2017-07-25 | 华灿光电(苏州）有限公司 | LED epitaxial slice and preparation method thereof |
| CN106206881B (en) * | 2016-08-31 | 2019-02-12 | 中联西北工程设计研究院有限公司 | A kind of preparation method of vertical structure LED blue light extension |
| CN107946419A (en) * | 2017-09-26 | 2018-04-20 | 华灿光电（浙江）有限公司 | A kind of LED epitaxial slice and its manufacture method |
| CN108336201B (en) * | 2018-01-25 | 2020-01-17 | 北京大学东莞光电研究院 | Novel patterned substrate |
| CN108321266A (en) * | 2018-02-01 | 2018-07-24 | 映瑞光电科技(上海)有限公司 | A kind of GaN base LED epitaxial structure and preparation method thereof |
| CN115360273B (en) * | 2022-06-22 | 2023-10-20 | 淮安澳洋顺昌光电技术有限公司 | Nitride semiconductor light-emitting element and manufacturing method thereof |
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| CN101183697A (en) * | 2007-12-10 | 2008-05-21 | 厦门大学 | Gallium nitride based LED epitaxial slice structure and method for preparing the same |
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| US7888696B2 (en) * | 2007-01-11 | 2011-02-15 | Lg Innotek Co., Ltd. | Semiconductor light emitting device and a method for manufacturing the same |
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| US7888696B2 (en) * | 2007-01-11 | 2011-02-15 | Lg Innotek Co., Ltd. | Semiconductor light emitting device and a method for manufacturing the same |
| US7638414B2 (en) * | 2007-03-06 | 2009-12-29 | Seoul Opto Device Co., Ltd. | Method of forming nitride semiconductor layer on patterned substrate and light emitting diode having the same |
| CN101183697A (en) * | 2007-12-10 | 2008-05-21 | 厦门大学 | Gallium nitride based LED epitaxial slice structure and method for preparing the same |
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