CN103531683A - Gallium nitride light emitting diode and preparation method thereof - Google Patents
Gallium nitride light emitting diode and preparation method thereof Download PDFInfo
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- CN103531683A CN103531683A CN201310434926.7A CN201310434926A CN103531683A CN 103531683 A CN103531683 A CN 103531683A CN 201310434926 A CN201310434926 A CN 201310434926A CN 103531683 A CN103531683 A CN 103531683A
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- H—ELECTRICITY
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- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0075—Processes for devices with an active region comprising only III-V compounds comprising nitride compounds
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
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Abstract
The invention discloses a gallium nitride light emitting diode and a preparation method thereof and belongs to the field of light emitting diodes. The method comprises the following steps: providing a foreign substrate, and depositing a first buffering layer on the foreign substrate by taking a first temperature as a growing temperature; depositing a second buffering layer on the first buffering layer and enabling the second buffering layer to grow at a second temperature from the time of beginning to grow to a first pre-set time, wherein the first temperature is lower than the second temperature and the differential value range of the first temperature and the second temperature is 410-460 DEG C; depositing a third buffering layer on the second buffering layer by taking a third temperature as the growing temperature, wherein the second temperature is lower than the third temperature; and sequentially depositing an N type contact layer, a light-emitting layer, an electronic barrier layer and a P type contact layer on the third buffering layer to finish the preparation of the gallium nitride light emitting diode. The light emitting diode is prepared by adopting the method. The growing starting temperature of the second buffering layer is between the growing temperature of the first buffering layer and the growing temperature of the third buffering layer and the second buffering layer has the buffering and protection effects on the third buffering layer.
Description
Technical field
The present invention relates to light-emitting diode (Light-Emitting Diode is called for short LED) field, particularly a kind of gallium nitride light-emitting diode and preparation method thereof.
Background technology
Gallium nitride (GaN) LED comprises substrate and in the main extension consisting of GaN of Grown.The principle that lattice based on substrate and extension need match, for GaN extension, desirable substrate is the monocrystalline of III group-III nitride.Yet present stage, the monocrystalline area developed was little and price is high, therefore generally adopted at present foreign substrate (for example Sapphire Substrate) growing GaN extension.
Between foreign substrate and GaN extension, inevitably there is lattice mismatch.In order to slow down the lattice mismatch between foreign substrate and GaN extension, first grown buffer layer on substrate conventionally, then on resilient coating growing GaN extension.Particularly, traditional resilient coating has adopted the GaN of 25nm or AlN as low temperature buffer layer, the high temperature GaN resilient coating of then growing on low temperature buffer layer.Low temperature buffer layer is discontinuous island structure, and high temperature GaN resilient coating first forms three dimensions growth on island structure, and three dimensions growth finishes rear formation two-dimensional growth.
In realizing process of the present invention, inventor finds that prior art at least exists following problem: growth high temperature buffer layer directly heats up after the low temperature buffer layer of having grown, be easier to form two-dimensional growth, cause being easy to couple together between island structure Zhong Daoyu island, thereby affect the three dimensional growth time of high temperature buffer layer, like this, be difficult to obtain high-quality GaN extension, and be difficult to control well the surface topography of GaN extension.
Summary of the invention
In order to solve the problem of prior art, the embodiment of the present invention provides a kind of gallium nitride light-emitting diode and preparation method thereof.Described technical scheme is as follows:
On the one hand, the embodiment of the present invention provides a kind of preparation method of gallium nitride light-emitting diode, and described method comprises:
Foreign substrate is provided, and take the first temperature as growth temperature, in described foreign substrate, deposit the first resilient coating;
On described the first resilient coating, deposit the second resilient coating, and described the second resilient coating is from starting to grow in first scheduled time with the second temperature growth, described the first temperature < described the second temperature, and the difference range of described the first temperature and described the second temperature is 410～460 ℃;
The 3rd temperature of take is growth temperature, on described the second resilient coating, deposits three buffer layer, described the second temperature < described the 3rd temperature;
On described three buffer layer, deposit successively N-type contact layer, luminescent layer, electronic barrier layer and P type contact layer, complete the preparation of described gallium nitride light-emitting diode.
Alternatively, describedly on described the first resilient coating, deposit the second resilient coating, and described the second resilient coating is from starting to grow in first scheduled time with the second temperature growth, comprising:
Take described the second temperature as constant temperature growth temperature, and to take described first scheduled time be growth time, on described the first resilient coating, deposit described the second resilient coating.
Alternatively, the span of described the second temperature is 930～980 ℃, and described first scheduled time is 700-1800 second.
Alternatively, describedly on described the first resilient coating, deposit the second resilient coating, and described the second resilient coating is from starting to grow in first scheduled time with the second temperature growth, comprising:
From starting to grow in described first scheduled time, with described the second temperature, on described the first resilient coating, deposit described the second resilient coating;
Finish to start within second scheduled time from described first scheduled time, growth temperature is increased to described the 3rd temperature gradually from described the second temperature, continue described the second resilient coating of deposition.
Alternatively, the span of described the second temperature is 930～980 ℃, and described first scheduled time is 700-1000 second, and described second scheduled time is 1-800 second.
Alternatively, described on described the first resilient coating, deposit the second resilient coating after, also comprise:
On described the second resilient coating, deposit the AlGaN layer of non-doping;
The 3rd temperature of take is growth temperature, on described the second resilient coating, deposits three buffer layer, comprising:
Described the 3rd temperature of take is growth temperature, on described AlGaN layer, deposits described three buffer layer.
Alternatively, described AlGaN layer be AlGaN GaN superlattice structure.
Alternatively, described the second resilient coating is GaN layer, and thickness is 0.5～1.0 μ m.
On the other hand, the embodiment of the present invention provides a kind of gallium nitride light-emitting diode, and described light-emitting diode adopts preceding method to prepare.
The beneficial effect that the technical scheme that the embodiment of the present invention provides is brought is: by take the first temperature as growth temperature, deposit the first resilient coating in foreign substrate, on the first resilient coating, deposit the second resilient coating, and the second resilient coating is from starting to grow in first scheduled time with the second temperature growth, the first temperature < the second temperature, and the difference range of the first temperature and the second temperature is 410～460 ℃, the 3rd temperature of take is growth temperature, on the second resilient coating, deposits three buffer layer, the second temperature < three temperature, the initial growth temperature of the second resilient coating is between the first resilient coating and the growth temperature of three buffer layer, three buffer layer is played to buffer protection function, on the discontinuous island structure that can avoid the 3rd cache layer to form at the first resilient coating relatively easily, form two-dimensional growth, extended the three dimensions growth time of three buffer layer, reduce the lattice mismatch between foreign substrate and GaN extension, effectively reduced extension dislocation density, thereby improved the crystal mass of GaN light-emitting diode, the antistatic intensity of GaN light-emitting diode and the luminous intensity of GaN based light-emitting diode have further been improved.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing of required use during embodiment is described is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is preparation method's flow chart of a kind of gallium nitride light-emitting diode of providing of the embodiment of the present invention;
Fig. 2-Fig. 3 is preparation method's flow chart of another gallium nitride light-emitting diode of providing of the embodiment of the present invention;
Fig. 4 is the structural representation of a kind of gallium nitride light-emitting diode of providing of the embodiment of the present invention.
Embodiment
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing, embodiment of the present invention is described further in detail.
Fig. 1 shows the preparation method of a kind of gallium nitride light-emitting diode that the embodiment of the present invention provides.Referring to Fig. 1, the method comprises:
Step 101: foreign substrate is provided, and take the first temperature as growth temperature, deposit the first resilient coating in foreign substrate.
Alternatively, the first temperature can be 520 ℃.
Step 102: deposit the second resilient coating on the first resilient coating, and the second resilient coating is from starting to grow in first scheduled time with the second temperature growth.
Wherein, the first temperature < the second temperature, and the difference range of the first temperature and the second temperature is 410～460 ℃.
Step 103: the 3rd temperature of take is growth temperature, deposits three buffer layer on the second resilient coating.
Wherein, the 3rd temperature > the second temperature.Alternatively, the 3rd temperature can be 1040 ℃.
Step 104: deposit successively N-type contact layer, luminescent layer, electronic barrier layer and P type contact layer on three buffer layer, complete the preparation of gallium nitride light-emitting diode.
The embodiment of the present invention, by take the first temperature as growth temperature, deposits the first resilient coating in foreign substrate, on the first resilient coating, deposit the second resilient coating, and the second resilient coating is from starting to grow in first scheduled time with the second temperature growth, the first temperature < the second temperature, and the difference range of the first temperature and the second temperature is 410～460 ℃, the 3rd temperature of take is growth temperature, on the second resilient coating, deposits three buffer layer, the second temperature < three temperature, the initial growth temperature of the second resilient coating is between the first resilient coating and the growth temperature of three buffer layer, three buffer layer is played to buffer protection function, on the discontinuous island structure that can avoid the 3rd cache layer to form at the first resilient coating relatively easily, form two-dimensional growth, extended the three dimensions growth time of three buffer layer, reduce the lattice mismatch between substrate and GaN extension, effectively reduced extension dislocation density, thereby improved the crystal mass of GaN light-emitting diode, the antistatic intensity of GaN light-emitting diode and the luminous intensity of GaN based light-emitting diode have further been improved.
Fig. 2 shows the preparation method of another gallium nitride light-emitting diode that the embodiment of the present invention provides.In embodiments of the present invention, Ga, Al, In and N source can adopt respectively trimethyl gallium (TMGa), trimethyl aluminium (TMAl), trimethyl indium (TMIn) and ammonia (NH3), carrier gas can be High Purity Hydrogen (H2) or nitrogen (N2), and N and P type dopant can adopt respectively silane (SiH4) and two luxuriant magnesium (Cp2Mg).Referring to Fig. 2, the method comprises:
Step 201: foreign substrate is provided.
Alternatively, foreign substrate is heat-treated under the H2 atmosphere of 1100 ℃, with clean surface.Heat treatment time can be 10 minutes.Foreign substrate includes but not limited to sapphire, Si and SiC substrate.
Step 202: take the first temperature as growth temperature, deposit the first resilient coating in foreign substrate.
Alternatively, the first temperature can be 520 ℃.Be down to 520 ℃ by aforementioned 1100 ℃, start to deposit the first resilient coating on substrate.The first resilient coating can be GaN layer or AlN layer, and thickness can be 25nm.
Step 203: deposit the second resilient coating on the first resilient coating, and the second resilient coating is from starting to grow in first scheduled time with the second temperature growth.
Wherein, the first temperature < the second temperature, and the difference range of the first temperature and the second temperature is 410～460 ℃.
Alternatively, this step 203 comprises: take the second temperature as constant temperature growth temperature, take for first scheduled time as growth time, deposit the second resilient coating on the first resilient coating.
Wherein, the span of the second temperature can be 930～980 ℃, and first scheduled time can be 700-1800 second.The growth time of the second resilient coating is grown (more than 700S), can promote the second resilient coating on discontinuous island structure, to carry out good three dimensional growth, slows down the lattice mismatch between foreign substrate and GaN extension.
Alternatively, this step 203 also comprises: take predetermined pressure as growth pressure, deposit the second resilient coating on the first resilient coating.This predetermined pressure can be 600-900 millibar (mbar).
Alternatively, deposit after the first resilient coating, rise to 950 ℃ by aforementioned 520 ℃, adjusting atmosphere pressures is 700mbar, starts to deposit the second resilient coating on the first resilient coating.In order to guarantee that the second resilient coating has enough space three-dimensional growth times, the growth time of the second resilient coating should be not less than 700S.The second resilient coating can be GaN layer, and thickness can be 0.5～1.0 μ m.
Step 204: the 3rd temperature of take is growth temperature, deposits three buffer layer on the second resilient coating.
Wherein, the 3rd temperature > the second temperature.
Alternatively, the 3rd temperature can be 1040 ℃.Rise to 1040 ℃ by aforementioned 950 ℃, start to deposit three buffer layer on the second resilient coating.Three buffer layer can be the non-Doped GaN layer of high temperature, and thickness can be 1.5 μ m.
Step 205: deposit successively N-type contact layer, luminescent layer, electronic barrier layer and P type contact layer on three buffer layer, complete the preparation of gallium nitride light-emitting diode.
Alternatively, complete after the growth of three buffer layer, the GaN layer of the Si doping that the 2.5 μ m that first grow on three buffer layer are thick, as N-type contact layer.Then cooling, the InGaN/GaN multiple quantum well layer in 5 cycles of growing on N-type contact layer is as luminescent layer.The emission wavelength of luminescent layer is 460nm, and the thickness of InGaN can be 2.5nm, and growth temperature can be 730 ℃, and the thickness of GaN can be 12nm, and growth temperature can be 800 ℃.Grow under 820 ℃ of growth temperatures again after quantum well layer growth the finishes P type Al0.18Ga0.82N electronic barrier layer of 30nm.Finally growth is the P type GaN contact layer of 120nm.
It should be noted that, in embodiments of the present invention, the deposition that above step is described includes but not limited to metal organic chemical vapor deposition.In addition, the preparation of gallium nitride light-emitting diode, except the epitaxial process that step 201-205 describes, also comprise that the epitaxial wafer obtaining after step 205 is finished cleans, the semiconducter process such as deposition, photoetching and etching, finally make the LED chip of single 12 * 30mil.
The embodiment of the present invention, by take the first temperature as growth temperature, deposits the first resilient coating in foreign substrate, on the first resilient coating, deposit the second resilient coating, and the second resilient coating is from starting to grow in first scheduled time with the second temperature growth, the first temperature < the second temperature, and the difference range of the first temperature and the second temperature is 410～460 ℃, the 3rd temperature of take is growth temperature, on the second resilient coating, deposits three buffer layer, the second temperature < three temperature, the initial growth temperature of the second resilient coating is between the first resilient coating and the growth temperature of three buffer layer, three buffer layer is played to buffer protection function, on the discontinuous island structure that can avoid the 3rd cache layer to form at the first resilient coating relatively easily, form two-dimensional growth, extended the three dimensions growth time of three buffer layer, reduce the lattice mismatch between substrate and GaN extension, effectively reduced extension dislocation density, thereby improved the crystal mass of GaN light-emitting diode, the antistatic intensity of GaN light-emitting diode and the luminous intensity of GaN based light-emitting diode have further been improved.
Fig. 3 shows the preparation method of another gallium nitride light-emitting diode that the embodiment of the present invention provides.Referring to Fig. 3, the method comprises:
Step 301: foreign substrate is provided.
This step 301, with step 201 in the embodiment shown in Fig. 2, does not repeat them here.
Step 302: take the first temperature as growth temperature, deposit the first resilient coating in foreign substrate.
This step 302, with step 202 in the embodiment shown in Fig. 2, does not repeat them here.
Step 303: deposit the second resilient coating on the first resilient coating, and the second resilient coating is from starting to grow in first scheduled time with the second temperature growth.
Wherein, the first temperature < the second temperature, and the difference range of the first temperature and the second temperature is 410～460 ℃.
Alternatively, this step 303 comprises: from starting to grow in first scheduled time, deposit the second resilient coating with the second temperature on the first resilient coating; Finish within second scheduled time since first scheduled time, growth temperature is increased to the 3rd temperature gradually from the second temperature, continue deposition the second resilient coating.
Alternatively, the span of the second temperature can be 930～980 ℃, and first scheduled time can be 700-1000S, and second scheduled time can be 1-800S.
Alternatively, this step 303 also comprises: take predetermined pressure as growth pressure, deposit the second resilient coating on the first resilient coating.This predetermined pressure can be 600-900 millibar (mbar).
Alternatively, deposit after the first resilient coating, adjusting atmosphere pressures is 700mbar, first growth temperature is remained on to 950 ℃, second resilient coating of growing within first scheduled time, then by growth temperature from 950 ℃ of gradual changes to 1040 ℃, continue to deposit the second resilient coating on the first resilient coating.The growth time of the second resilient coating should be not less than 700S.The second resilient coating can be GaN layer, and thickness can be 0.5～1.0 μ m.
Alternatively, this step 303 also comprises: since the second resilient coating, grow in the time period that finishes growth, growth pressure is reduced to predetermined minimum pressure gradually from predetermined maximum pressure, deposit the second resilient coating on the first resilient coating.
Wherein, predetermined maximum pressure can be 900mbar, and predetermined minimum pressure can be 600mbar.
The growth temperature of the second resilient coating is gradient to high temperature from low temperature, and on the one hand, the low temperature starting most contributes to protect the discontinuous island structure of the first buffer growth, promotes the space three-dimensional growth of the second resilient coating, improves the surface topography of LED extension.On the other hand, be gradient to after high temperature, temperature is transitioned into three buffer layer well, can relax the stress between the second resilient coating and three buffer layer, reduces dislocation density, improves the crystal mass of LED, increases the antistatic intensity of LED and luminosity.
Step 304: the AlGaN layer that deposits non-doping on the second resilient coating.
Alternatively, the thickness of AlGaN layer can be 10～30nm.After the second resilient coating has been grown, follow the non-doped with Al GaN of long 20nm on the second resilient coating.
Alternatively, AlGaN layer can be AlGaN GaN superlattice structure, for example the superlattice structure in two cycles: AlGaN GaN AlGaN GaN.
AlGaN layer has stopped the extension of the first resilient coating dislocation effectively, thereby improves the growth quality of GaN LED, reduces the leakage current of LED.
Step 305: the 3rd temperature of take is growth temperature, deposits three buffer layer on AlGaN layer.
This step 305, with step 204 in the embodiment shown in Fig. 2, does not repeat them here.
Step 306: deposit successively N-type contact layer, luminescent layer, electronic barrier layer and P type contact layer on three buffer layer, complete the preparation of gallium nitride light-emitting diode.
This step 306, with step 205 in the embodiment shown in Fig. 2, does not repeat them here.
The embodiment of the present invention, by take the first temperature as growth temperature, deposits the first resilient coating in foreign substrate, on the first resilient coating, deposit the second resilient coating, and the second resilient coating is from starting to grow in first scheduled time with the second temperature growth, the first temperature < the second temperature, and the difference range of the first temperature and the second temperature is 410～460 ℃, the 3rd temperature of take is growth temperature, on the second resilient coating, deposits three buffer layer, the second temperature < three temperature, the initial growth temperature of the second resilient coating is between the first resilient coating and the growth temperature of three buffer layer, three buffer layer is played to buffer protection function, on the discontinuous island structure that can avoid the 3rd cache layer to form at the first resilient coating relatively easily, form two-dimensional growth, extended the three dimensions growth time of three buffer layer, reduce the lattice mismatch between substrate and GaN extension, effectively reduced extension dislocation density, thereby improved the crystal mass of GaN light-emitting diode, the antistatic intensity of GaN light-emitting diode and the luminous intensity of GaN based light-emitting diode have further been improved.
Fig. 4 shows a kind of gallium nitride light-emitting diode that the embodiment of the present invention provides, and this gallium nitride light-emitting diode can adopt the method shown in Fig. 1,2 or 3 to prepare.Referring to Fig. 4, this light-emitting diode comprises: substrate 401, the first resilient coating 402, the second resilient coating 403, three buffer layer 404, N-type contact layer 405, luminescent layer 406, electronic barrier layer 407 and P type contact layer 408.
Alternatively, the growth temperature of growth temperature < the three buffer layer 404 of growth temperature < the second resilient coating 403 of the first resilient coating 402.And the difference range of the growth temperature of the growth temperature of the first resilient coating 402 and the second resilient coating 403 is 410～460 ℃
Alternatively, the growth temperature of the second resilient coating 403 can be constant temperature, and when being constant temperature, the scope of growth temperature can be 930～980 ℃, and growth time can be 700-1800S, and growth pressure can be 600-900mbar.
Alternatively, the growth temperature of the second resilient coating 403 can also raise gradually.
Alternatively, the second resilient coating 403 can be GaN layer, and thickness can be 0.5～1.0 μ m.
Alternatively, this light-emitting diode also comprises the AlGaN layer 403a of non-doping, and this AlGaN layer 403a is between the second resilient coating 403 and three buffer layer 404.
Alternatively, this AlGaN layer 403a can be AlGaN GaN superlattice structure.
The embodiment of the present invention, by take the first temperature as growth temperature, deposits the first resilient coating in foreign substrate, on the first resilient coating, deposit the second resilient coating, and the second resilient coating is from starting to grow in first scheduled time with the second temperature growth, the first temperature < the second temperature, and the difference range of the first temperature and the second temperature is 410～460 ℃, the 3rd temperature of take is growth temperature, on the second resilient coating, deposits three buffer layer, the second temperature < three temperature, the initial growth temperature of the second resilient coating is between the first resilient coating and the growth temperature of three buffer layer, three buffer layer is played to buffer protection function, on the discontinuous island structure that can avoid the 3rd cache layer to form at the first resilient coating relatively easily, form two-dimensional growth, extended the three dimensions growth time of three buffer layer, reduce the lattice mismatch between substrate and GaN extension, effectively reduced extension dislocation density, thereby improved the crystal mass of GaN light-emitting diode, the antistatic intensity of GaN light-emitting diode and the luminous intensity of GaN based light-emitting diode have further been improved.
The invention described above embodiment sequence number, just to describing, does not represent the quality of embodiment.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (9)
1. a preparation method for gallium nitride light-emitting diode, is characterized in that, described method comprises:
Foreign substrate is provided, and take the first temperature as growth temperature, in described foreign substrate, deposit the first resilient coating;
On described the first resilient coating, deposit the second resilient coating, and described the second resilient coating is from starting to grow in first scheduled time with the second temperature growth, described the first temperature < described the second temperature, and the difference range of described the first temperature and described the second temperature is 410～460 ℃;
The 3rd temperature of take is growth temperature, on described the second resilient coating, deposits three buffer layer, described the second temperature < described the 3rd temperature;
On described three buffer layer, deposit successively N-type contact layer, luminescent layer, electronic barrier layer and P type contact layer, complete the preparation of described gallium nitride light-emitting diode.
2. method according to claim 1, is characterized in that, describedly on described the first resilient coating, deposits the second resilient coating, and described the second resilient coating is from starting to grow in first scheduled time with the second temperature growth, comprising:
Take described the second temperature as constant temperature growth temperature, and to take described first scheduled time be growth time, on described the first resilient coating, deposit described the second resilient coating.
3. method according to claim 2, is characterized in that, the span of described the second temperature is 930～980 ℃, and described first scheduled time is 700-1800 second.
4. method according to claim 1, is characterized in that, describedly on described the first resilient coating, deposits the second resilient coating, and described the second resilient coating is from starting to grow in first scheduled time with the second temperature growth, comprising:
From starting to grow in described first scheduled time, with described the second temperature, on described the first resilient coating, deposit described the second resilient coating;
Finish to start within second scheduled time from described first scheduled time, growth temperature is increased to described the 3rd temperature gradually from described the second temperature, continue described the second resilient coating of deposition.
5. method according to claim 4, is characterized in that, the span of described the second temperature is 930～980 ℃, and described first scheduled time is 700-1000 second, and described second scheduled time is 1-800 second.
6. according to the method described in claim 1-5 any one, it is characterized in that, described on described the first resilient coating, deposit the second resilient coating after, also comprise:
On described the second resilient coating, deposit the AlGaN layer of non-doping;
The 3rd temperature of take is growth temperature, on described the second resilient coating, deposits three buffer layer, comprising:
Described the 3rd temperature of take is growth temperature, on described AlGaN layer, deposits described three buffer layer.
7. method according to claim 6, is characterized in that, described AlGaN layer be AlGaN GaN superlattice structure.
8. method according to claim 7, is characterized in that, described the second resilient coating is GaN layer, and thickness is 0.5～1.0 μ m.
9. a gallium nitride light-emitting diode, is characterized in that, described light-emitting diode adopts the method described in claim 1-6 any one to prepare.
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