CN103078025A - Light-emitting diode (LED) epitaxial wafer and manufacturing method thereof - Google Patents
Light-emitting diode (LED) epitaxial wafer and manufacturing method thereof Download PDFInfo
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- CN103078025A CN103078025A CN2013100302238A CN201310030223A CN103078025A CN 103078025 A CN103078025 A CN 103078025A CN 2013100302238 A CN2013100302238 A CN 2013100302238A CN 201310030223 A CN201310030223 A CN 201310030223A CN 103078025 A CN103078025 A CN 103078025A
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Abstract
The invention discloses a light-emitting diode (LED) epitaxial wafer and a manufacturing method thereof. The manufacturing method of the LED epitaxial wafer comprises the following steps of supplying a substrate; developing a first gallium nitride layer on the substrate; developing a stress release layer on the first gallium nitride layer; developing a protecting layer on the stress release layer, wherein the lattice structure of the protecting layer is the same as that of the first gallium nitride layer; and developing a second gallium nitride layer on the protecting layer, and meanwhile decomposing the stress release layer to be a stress release layer with the lattice structure broken. The interaction between the protecting layer and the first gallium nitride layer is eliminated by the stress release layer with the lattice structure broken; and the lattice structure of the protecting layer is the same as that of the first gallium nitride layer, so that a template is supplied for the development of the second gallium nitride layer. The second gallium nitride layer can be developed to be relatively thick, so that the problem that fissures formed in gallium nitride materials cannot be effectively eliminated by the prior method for developing the gallium nitride materials on a silicon substrate is solved, and the performance and the yield of devices are improved.
Description
Technical field
The present invention relates to LED manufacturing technology field, relate in particular to a kind of LED epitaxial wafer and manufacture method thereof.
Background technology
Environmental protection is an important trend of modern illumination development, and the birth of LED technology and development are causing the revolution of throwing light on for the second time.Compare with conventional light source, LED have the life-span long, light efficiency is high, low in energy consumption, volume is little, the free advantage such as integrated.The applications such as out of doors demonstration, Landscape Lighting, TV are backlight, room lighting replace conventional light source gradually becomes main flow.
At present, LED adopts epitaxially grown method to be produced on the substrate, and this is because occurring in nature does not have natural gallium nitride material.Backing material commonly used has sapphire, carborundum (SiC), silicon (Si) etc.This wherein, Sapphire Substrate has occupied shares a large amount of in the market because suitable price, ripe process technology are widely used in light-emitting diode.But sapphire thermal conductivity is very low, only has 0.5W/cmK, and the LED under high current density work if the heat that produces can not conduct out from device rapidly, will cause the device luminous efficiency to reduce even inefficacy.The lattice constant of carborundum and gallium nitride approaches, and the lattice mismatch of this bi-material only has 3%, therefore the high GaN material of easier acquisition crystalline quality on the SiC substrate.But the silicon carbide substrates cost of manufacture is high, processing is relatively immature, causes price to be higher than sapphire far away, only has several LED companies to use.The silicon substrate price is the most cheap, and the growth of silicon substrate, processing technology are the most ripe, and the substrate dimension that can make is maximum, also is the larger substrates of a kind of potentiality therefore.
The difficult point of epitaxial growth gallium nitride material is that the thermal coefficient of expansion of GaN and silicon substrate has very big-difference on silicon substrate, high temperature when the GaN layer of extension is from growth after surpassing 1 micron can produce a lot of crackles when being reduced to room temperature, finally causes the GaN fault in material of extension too much can't use.And usually when making blue green light LED, need the thickness of gallium nitride material will be more than 3 microns.For this problem, there is Many researchers to propose different schemes: in the middle of the gallium nitride growth, to insert the aln layer of a low temperature, can effectively eliminate this crackle; But the gallium nitride thickness above this low temperature aln layer is also limited, can only guarantee that top gallium nitride thickness is at 1 micron.Thicker flawless gallium nitride be can provide by inserting multilayer low temperature AI N layer, but complexity and the cost of technique increased.Another kind method is to make the figure measure-alike with final LED at silicon substrate in advance, and each led chip is separated in advance, also can reduce the quantity of crackle, but has also increased complexity and the cost of technique.
Summary of the invention
The invention provides a kind of LED epitaxial wafer and manufacture method thereof, to solve the problem that cracks in the gallium nitride material of growing on the silicon substrate.
For overcoming the above problems, the invention provides a kind of manufacture method of LED epitaxial wafer, comprising:
Substrate is provided;
At described Grown the first gallium nitride layer;
At described the first gallium nitride layer growth stress releasing layer;
At described stress release layer growth protecting layer, described protective layer lattice structure is consistent with the first gallium nitride layer;
Growth regulation two gallium nitride layers on described protective layer, simultaneously, described stress release layer is decomposed to form the destroyed stress release layer of lattice structure.
Optionally, before growth the first gallium nitride layer, also be included in the step of described Grown aln layer.
Optionally, before the Grown aluminum nitride buffer layer, also comprise: substrate under 1000 ℃ ~ 1200 ℃ temperature, is toasted in hydrogen environment.
Optionally, utilize MOCVD technique grow described aluminum nitride buffer layer, the first gallium nitride layer, stress release layer, protective layer and the second gallium nitride layer.
Optionally, the growth technique of described aluminum nitride buffer layer carries out under 1000 ℃ ~ 1200 ℃ temperature, and process gas is trimethyl aluminium and ammonia, and the thickness of the aluminum nitride buffer layer of growth is 10nm ~ 200nm.
Optionally, the growth technique of described the first gallium nitride layer carries out under 1000 ℃ ~ 1200 ℃ temperature, and process gas is trimethyl gallium and ammonia, and the thickness of the first gallium nitride layer of growth is 200nm ~ 1000nm.
Optionally, the material of described stress release layer is InGaN.
Optionally, being grown under 500 ℃ ~ 800 ℃ the temperature of described InGaN carried out, process gas is trimethyl indium, trimethyl gallium and ammonia, and wherein the amount of substance of indium is more than or equal to 10% of indium and the total amount of substance of gallium, and the thickness of growing indium nitride gallium is 200nm ~ 1000nm.
Optionally, the material of described protective layer is aluminium gallium nitride alloy.
Optionally, being grown under 500 ℃ ~ 800 ℃ the temperature of described aluminium gallium nitride alloy carried out, and wherein the amount of substance of aluminium is more than or equal to 20% of the total amount of substance of aluminium plus gallium, and the thickness of growing aluminum nitride gallium is 100nm ~ 500nm.
Optionally, it is characterized in that the growth technique of described the second gallium nitride layer carries out under 1000 ℃ ~ 1200 ℃ temperature, process gas is trimethyl aluminium and ammonia, and the thickness of the second gallium nitride layer of growth is 2000nm ~ 10000nm.
Another side of the present invention also provides a kind of LED epitaxial wafer; utilize the manufacture method of above-mentioned LED epitaxial wafer to form, comprising: substrate, grow in destroyed stress release layer, protective layer and the second gallium nitride layer of the first gallium nitride layer, lattice structure on the described substrate successively.
Optionally, between described substrate and the first gallium nitride layer, also comprise aluminum nitride buffer layer.
Optionally, the thickness of the destroyed stress release layer of described lattice structure is 10nm ~ 1000nm.
Optionally, the thickness of described protective layer is 100nm ~ 500nm.
Optionally, the material of described protective layer is aluminium gallium nitride alloy.
Optionally, in the described aluminium gallium nitride alloy amount of substance of aluminium more than or equal to 20% of the total amount of substance of aluminium plus gallium.
Optionally, the thickness 2000nm ~ 10000nm of the second gallium nitride layer.
The invention provides a kind of LED epitaxial wafer and manufacture method thereof, described LED epitaxial wafer comprises: substrate, grow in the first gallium nitride layer, stress release layer, protective layer and the second gallium nitride layer on the described substrate successively.Because described stress release layer decomposes under the temperature of growth regulation two gallium nitride layers; its crystal structure is destroyed; thereby eliminated the interaction of described protective layer and the first gallium nitride layer; so that second gallium nitride layer of growing at protective layer can reach thicker thickness; solved existing on silicon substrate the method for growing gallium nitride material can't effectively eliminate in the gallium nitride material problem that forms crackle, promoted performance of devices and yield.
Description of drawings
Fig. 1 is the flow chart of manufacture method of the LED epitaxial wafer of the embodiment of the invention;
Fig. 2 A ~ 2F is the cross-sectional view of each step of manufacture method of the LED epitaxial wafer of the embodiment of the invention.
Embodiment
In background technology, mention and since existing on silicon substrate the method for growing gallium nitride material can't effectively eliminate in the gallium nitride material problem that forms crackle, restricted the thickness of gallium nitride material, and affected performance of devices and yield.
For this reason, the invention provides a kind of LED epitaxial wafer and manufacture method thereof, described LED epitaxial wafer comprises: substrate, grow in the first gallium nitride layer on the described substrate, stress release layer, protective layer and the second gallium nitride layer successively.Because described stress release layer decomposes under the temperature of growth regulation two gallium nitride layers; its crystal structure is destroyed; thereby eliminated the interaction of described protective layer and the first gallium nitride layer, so that second gallium nitride layer of growing on protective layer can reach thicker thickness.
Below in conjunction with accompanying drawing the present invention is described in more detail, has wherein represented the preferred embodiments of the present invention, should the described those skilled in the art of understanding can revise the present invention described here, and still realize advantageous effects of the present invention.Therefore, following description is appreciated that extensively knowing for those skilled in the art, and not as limitation of the present invention.
For clear, whole features of practical embodiments are not described.In the following description, be not described in detail known function and structure, the confusion because they can make the present invention owing to unnecessary details.Will be understood that in the exploitation of any practical embodiments, must make a large amount of implementation details to realize developer's specific objective, for example according to relevant system or relevant commercial restriction, change into another embodiment by an embodiment.In addition, will be understood that this development may be complicated and time-consuming, but only be routine work to those skilled in the art.
In the following passage, with way of example the present invention is described more specifically with reference to accompanying drawing.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 in order to convenient, the purpose of the aid illustration embodiment of the invention lucidly.
Please refer to Fig. 1, the flow chart of the LED epitaxial wafer manufacture method that it provides for the embodiment of the invention, described method comprises the steps:
Step S31 provides substrate;
Step S32 is at described Grown the first gallium nitride layer;
Step S33 is at described the first gallium nitride layer growth stress releasing layer;
Step S34, at described stress release layer growth protecting layer, described protective layer lattice structure is consistent with the first gallium nitride layer;
Step S35, growth regulation two gallium nitride layers on described protective layer, simultaneously, described stress release layer is decomposed to form the destroyed stress release layer of lattice structure.
Preferably, the growth the first gallium nitride layer before, also at Grown aluminum nitride buffer layer.In the present embodiment, the growth technique of described aluminum nitride buffer layer, the first gallium nitride layer, stress release layer, protective layer and the second gallium nitride layer is the MOCVD(metal-organic chemical vapor deposition equipment) technique, all in the MOCVD board, carry out.
With reference to Fig. 2 A, execution in step S31 provides substrate 101.Preferably, before carrying out subsequent epitaxial growth process, also comprise the step that described substrate 101 is cleaned.Its detailed process is as follows: described substrate 101 is put into the metal-organic chemical vapor deposition equipment board, under 1000 ℃ ~ 1200 ℃ temperature, pass into hydrogen, to remove oxide layer and the pollutant on substrate 101 surfaces.
With reference to Fig. 2 B, growing aluminum nitride resilient coating 102 on described substrate 101.Concrete, under 1000 ℃ ~ 1200 ℃ temperature, carrying out the growth of aluminum nitride buffer layer 102, process gas is preferably trimethyl aluminium and ammonia, and the thickness of the aluminum nitride buffer layer 102 of growth is 10nm ~ 200nm.
With reference to Fig. 2 C, execution in step S32 is at described aluminum nitride buffer layer 102 growths the first gallium nitride layer 103.Concrete, under 1000 ℃ ~ 1200 ℃ temperature, carrying out the growth of the first gallium nitride layer 103, process gas is preferably trimethyl gallium and ammonia, and the thickness of the first gallium nitride layer 103 of growth is 200nm ~ 1000nm.
With reference to Fig. 2 D, execution in step S33 is at described the first gallium nitride layer 103 growth stress releasing layers 104.Preferably, the material of described Stress Release 104 is InGaN.Concrete, in the present embodiment, being grown under 500 ℃ ~ 800 ℃ the temperature of described InGaN carried out, process gas is trimethyl indium, trimethyl gallium and ammonia, wherein the amount of substance of indium is more than or equal to 10% of indium and the total amount of substance of gallium, the thickness of growing indium nitride gallium is 200nm ~ 1000nm, and one of them better thickness is 500nm.Certainly, those skilled in the art can select process gas according to real needs, for example select other alkyl derivatives, aryl derivatives or the hydroxy derivatives of indium.
With reference to Fig. 2 E, execution in step S34, at described stress release layer 104 growth protecting layers 105, described protective layer lattice structure is consistent with the first gallium nitride layer.Preferably, the material of described protective layer 105 is aluminium gallium nitride alloy.Concrete, being grown under 500 ℃ ~ 800 ℃ the temperature of described aluminium gallium nitride alloy carried out, and the amount of substance of aluminium is more than or equal to 20% of the total amount of substance of aluminium plus gallium in the better embodiment, and the thickness of growing aluminum nitride gallium is 100nm ~ 500nm.
With reference to Fig. 2 F, execution in step S35, growth regulation two gallium nitride layers 106 on described protective layer 105, simultaneously, described stress release layer 104 is decomposed to form the destroyed stress release layer 104 ' of lattice structure.The growth technique of described the second gallium nitride layer 106 carries out under 1000 ℃ ~ 1200 ℃ temperature, and process gas is trimethyl aluminium and ammonia.Stress release layer 104 decomposes under this temperature, forms the destroyed stress release layer 104 ' of lattice structure, so that protective layer 105 and the 103 mutual effects of the first gallium nitride layer are eliminated.And the lattice structure of protective layer 105 is consistent with the first gallium nitride layer 103, for 106 growths of the second gallium nitride layer provide template.Therefore the second gallium nitride layer 106 thicker thickness of can growing for example is 2000nm ~ 10000nm.
Another side of the present invention; a kind of LED epitaxial wafer of being made by said method also is provided; please refer to Fig. 2 F; the structural representation of the LED epitaxial wafer that it provides for the embodiment of the invention, described LED epitaxial wafer comprises: substrate 101, grow in destroyed stress release layer 104 ', protective layer 105 and the second gallium nitride layer 106 of the first gallium nitride layer 103, lattice structure on the described substrate 101 successively.Preferably, between described substrate 101 and described the first gallium nitride layer 103, also comprise aluminum nitride buffer layer 102,
Concrete, the thickness of described aluminum nitride buffer layer 102 is 10nm ~ 200nm, described the first gallium nitride layer 103 thickness are 200nm ~ 1000nm.The thickness of described stress release layer 104 is 10nm ~ 1000nm, material is preferably InGaN, wherein the amount of substance of indium is more than or equal to 10% of indium and the total amount of substance of gallium, and more excellent, the amount of substance of indium is more than or equal to 50% of indium and the total amount of substance of gallium in the described InGaN.When growth regulation two gallium nitride layer 106, described stress release layer 104 decomposes like this, and the destroyed stress release layer 104 ' of formation lattice structure has been eliminated the interaction between described protective layer 105 and the first gallium nitride layer 103.The thickness of described protective layer 105 is 100nm ~ 500nm, and material is preferably aluminium gallium nitride alloy, and is more excellent, and the amount of substance of aluminium is more than or equal to 20% of the total amount of substance of aluminium plus gallium in the described aluminium gallium nitride alloy.Stress release layer 104 decompose crystal structures destroyed after because protective layer 105 has the lattice structure consistent with the first gallium nitride layer 103, it can continue as 106 growths of the second gallium nitride layer template is provided.Because the interaction between described protective layer 105 and the first gallium nitride layer 103 is eliminated by stress release layer 104, the second gallium nitride layer 106 that forms at protective layer 105 can obtain thicker thickness, for example 2000nm ~ 10000nm.Therefore overcome existing on silicon substrate the method for growing gallium nitride material can't effectively eliminate the problem that forms crackle in the gallium nitride material, promoted performance of devices and yield.
Certainly, in the structure of the epitaxial wafer of present embodiment or step, also comprise some known structure or steps, as, the step of the step of epitaxial growth multiple quantum well active layer, extension ITO layer etc., the present invention does not relate to the improvement to these structures and step, those skilled in the art can add to these steps in the solution of the present invention according to the common practise of this area, do not repeat them here.
In sum, the invention provides a kind of LED epitaxial wafer and manufacture method thereof, described LED epitaxial wafer comprises: substrate, grow in aluminum nitride buffer layer, the first gallium nitride layer, stress release layer, protective layer and the second gallium nitride layer on the described substrate successively.Because described stress release layer decomposes under the temperature of growth regulation two gallium nitride layers; its crystal structure is destroyed; thereby eliminated the interaction of described protective layer and the first gallium nitride layer, so that second gallium nitride layer of growing at protective layer can reach thicker thickness.
Obviously, those skilled in the art can carry out various changes and modification to the present 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 (18)
1. the manufacture method of a LED epitaxial wafer comprises:
Substrate is provided;
At described Grown the first gallium nitride layer;
At described the first gallium nitride layer growth stress releasing layer;
At described stress release layer growth protecting layer, described protective layer lattice structure is consistent with the first gallium nitride layer;
Growth regulation two gallium nitride layers on described protective layer, simultaneously, described stress release layer is decomposed to form the destroyed stress release layer of lattice structure.
2. the manufacture method of LED epitaxial wafer as claimed in claim 1 is characterized in that, also is included in the step of described Grown aln layer before growth the first gallium nitride layer.
3. the manufacture method of LED epitaxial wafer as claimed in claim 2 is characterized in that, also comprises before the Grown aluminum nitride buffer layer: substrate under 1000 ℃ ~ 1200 ℃ temperature, is toasted in hydrogen environment.
4. the manufacture method of LED epitaxial wafer as claimed in claim 2 is characterized in that, utilizes MOCVD technique grow described aluminum nitride buffer layer, the first gallium nitride layer, stress release layer, protective layer and the second gallium nitride layer.
5. the manufacture method of LED epitaxial wafer as claimed in claim 2, it is characterized in that, the growth technique of described aluminum nitride buffer layer carries out under 1000 ℃ ~ 1200 ℃ temperature, and process gas is trimethyl aluminium and ammonia, and the thickness of the aluminum nitride buffer layer of growth is 10nm ~ 200nm.
6. the manufacture method of LED epitaxial wafer as claimed in claim 4, it is characterized in that, the growth technique of described the first gallium nitride layer carries out under 1000 ℃ ~ 1200 ℃ temperature, and process gas is trimethyl gallium and ammonia, and the thickness of the first gallium nitride layer of growth is 200nm ~ 1000nm.
7. the manufacture method of LED epitaxial wafer as claimed in claim 4 is characterized in that, the material of described stress release layer is InGaN.
8. the manufacture method of LED epitaxial wafer as claimed in claim 7, it is characterized in that, being grown under 500 ℃ ~ 800 ℃ the temperature of described InGaN carried out, process gas is trimethyl indium, trimethyl gallium and ammonia, wherein the amount of substance of indium is more than or equal to 10% of indium and the total amount of substance of gallium, and the thickness of growing indium nitride gallium is 200nm ~ 1000nm.
9. the manufacture method of LED epitaxial wafer as claimed in claim 4 is characterized in that, the material of described protective layer is aluminium gallium nitride alloy.
10. the manufacture method of LED epitaxial wafer as claimed in claim 9, it is characterized in that, being grown under 500 ℃ ~ 800 ℃ the temperature of described aluminium gallium nitride alloy carried out, and wherein the amount of substance of aluminium is more than or equal to 20% of the total amount of substance of aluminium plus gallium, and the thickness of growing aluminum nitride gallium is 100nm ~ 500nm.
11. the manufacture method of LED epitaxial wafer as claimed in claim 4, it is characterized in that, the growth technique of described the second gallium nitride layer carries out under 1000 ℃ ~ 1200 ℃ temperature, and process gas is trimethyl aluminium and ammonia, and the thickness of the second gallium nitride layer of growth is 2000nm ~ 10000nm.
12. LED epitaxial wafer; utilize the manufacture method of LED epitaxial wafer as claimed in claim 1 to form, described LED epitaxial wafer comprises: substrate, be positioned at destroyed stress release layer, protective layer and the second gallium nitride layer of the first gallium nitride layer, lattice structure on the described substrate successively.
13. LED epitaxial wafer as claimed in claim 12 is characterized in that, also comprises aluminum nitride buffer layer between described substrate and the first gallium nitride layer.
14. LED epitaxial wafer as claimed in claim 12 is characterized in that, the thickness of the stress release layer that described lattice structure is destroyed is 10nm ~ 1000nm.
15. LED epitaxial wafer as claimed in claim 12 is characterized in that, the thickness of described protective layer is 100nm ~ 500nm.
16. LED epitaxial wafer as claimed in claim 15 is characterized in that, the material of described protective layer is aluminium gallium nitride alloy.
17. LED epitaxial wafer as claimed in claim 16 is characterized in that the amount of substance of aluminium is more than or equal to 20% of the total amount of substance of aluminium plus gallium in the described aluminium gallium nitride alloy.
18. LED epitaxial wafer as claimed in claim 12 is characterized in that, the thickness of described the second gallium nitride layer is 2000nm ~ 10000nm.
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| US6495867B1 (en) * | 2000-07-26 | 2002-12-17 | Axt, Inc. | InGaN/AlGaN/GaN multilayer buffer for growth of GaN on sapphire |
| CN101702418A (en) * | 2009-10-23 | 2010-05-05 | 山东华光光电子有限公司 | GaN-based LED chip extending and growing method for reducing dislocation defects |
| CN102569567A (en) * | 2012-03-21 | 2012-07-11 | 中国科学院半导体研究所 | Method for growing nitride light-emitting diode (LED) epitaxial structure |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6495867B1 (en) * | 2000-07-26 | 2002-12-17 | Axt, Inc. | InGaN/AlGaN/GaN multilayer buffer for growth of GaN on sapphire |
| CN101702418A (en) * | 2009-10-23 | 2010-05-05 | 山东华光光电子有限公司 | GaN-based LED chip extending and growing method for reducing dislocation defects |
| CN102569567A (en) * | 2012-03-21 | 2012-07-11 | 中国科学院半导体研究所 | Method for growing nitride light-emitting diode (LED) epitaxial structure |
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