CN109768130A - A kind of gallium nitride based LED epitaxial slice and preparation method thereof - Google Patents
A kind of gallium nitride based LED epitaxial slice and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of gallium nitride based LED epitaxial slices and preparation method thereof, belong to technical field of semiconductors.The gallium nitride based LED epitaxial slice includes substrate, n type semiconductor layer, active layer and p type semiconductor layer, the n type semiconductor layer, the active layer and the p type semiconductor layer stack gradually over the substrate, and the material of the p type semiconductor layer is using the GaN for adulterating Be.The present invention in p type semiconductor layer by using Be as P-type dopant, the acceptor ionization energy of Be is about 60meV, acceptor ionization energy (about 250meV) much smaller than Mg, compared with use Mg is as P-type dopant, hole can be more easily obtained, hole concentration is improved, improves electrons and holes in active layer and injects asymmetric situation, the luminous efficiency of LED is avoided in the case where Injection Current increases, is quickly reduced instead.
Description
Technical field
The present invention relates to technical field of semiconductors, in particular to a kind of gallium nitride based LED epitaxial slice and its production
Method.
Background technique
Light emitting diode (English: Light Emitting Diode, referred to as: LED) it is a kind of semi-conductor electricity that can be luminous
Subcomponent.Due to the improvement that the increased quality and device of current gallium nitride (GaN) base semiconductor material manufacture, GaN base LED is expected to
Replace traditional incandescent lamp and fluorescent lamp.
Epitaxial wafer is the primary finished product in LED preparation process.Existing LED epitaxial wafer include substrate, n type semiconductor layer,
Active layer and p type semiconductor layer, n type semiconductor layer, active layer and p type semiconductor layer stack gradually on substrate.Substrate is used for
Growing surface is provided for epitaxial material, n type semiconductor layer is used to provide the electronics for carrying out recombination luminescence, and p type semiconductor layer is used for
The hole for carrying out recombination luminescence is provided, the radiation recombination that active layer is used to carry out electrons and holes shines.
In the implementation of the present invention, the inventor finds that the existing technology has at least the following problems:
P type semiconductor layer generallys use Mg and carries out p-type doping, but the activation rate of Mg is very low, is unable to reach expected mix
Miscellaneous effect causes to inject the electron amount that the number of cavities in active layer can be less than in injection active layer, ultimately causes the hair of LED
Light efficiency quickly reduces instead in the case where Injection Current increases.
Summary of the invention
The embodiment of the invention provides a kind of gallium nitride based LED epitaxial slice and preparation method thereof, it is able to solve existing
There is the problem of technology.The technical solution is as follows:
On the one hand, the embodiment of the invention provides a kind of gallium nitride based LED epitaxial slice, the gallium nitride base hairs
Optical diode epitaxial wafer includes substrate, n type semiconductor layer, active layer and p type semiconductor layer, and the n type semiconductor layer described has
Active layer and the p type semiconductor layer stack gradually over the substrate, and the material of the p type semiconductor layer is using doping Be's
GaN。
Optionally, the doping concentration of Be is 10 in the p type semiconductor layer18/cm3~1020/cm3。
Optionally, the gallium nitride light-emitting diode epitaxial wafer further includes insert layer, and the material of the insert layer, which uses, to be mixed
The Al of miscellaneous MgxInyGa1-x-y0.3,0 < y < 0.1 of N, 0.1 < x <, the insert layer are arranged in the n type semiconductor layer and institute
It states between active layer.
Preferably, the doping concentration of Mg is 1/200 of the doping concentration of Be in the p type semiconductor layer in the insert layer
~1/50.
It is highly preferred that the doping concentration of Mg is 10 in the insert layer16/cm3~1018/cm3。
Preferably, the insert layer with a thickness of 5nm~15nm.
Optionally, the gallium nitride light-emitting diode epitaxial wafer further includes electronic barrier layer, the material of the electronic barrier layer
Material is using the Al for adulterating MgzGa1-zN, 0.1 < z < 0.6, the electronic barrier layer setting is in the active layer and the p-type half
Between conductor layer.
Preferably, the gallium nitride light-emitting diode epitaxial wafer further includes low temperature P-type layer, the material of the low temperature P-type layer
Using the GaN of doping Be, the low temperature P-type layer is arranged between the active layer and the electronic barrier layer.
It is highly preferred that in the low temperature P-type layer doping concentration of Be and Be in the p type semiconductor layer doping concentration phase
Together.
On the other hand, the embodiment of the invention provides a kind of production method of gallium nitride based LED epitaxial slice, institutes
Stating production method includes:
One substrate is provided；
N type semiconductor layer, active layer and p type semiconductor layer are successively grown over the substrate；
Wherein, the material of the p type semiconductor layer is using the GaN for adulterating Be.
Technical solution provided in an embodiment of the present invention has the benefit that
By using Be as P-type dopant in p type semiconductor layer, the acceptor ionization energy of Be is about 60meV, is much smaller than
The acceptor ionization energy (about 250meV) of Mg can more easily obtain hole, mention compared with use Mg is as P-type dopant
High hole concentration improves electrons and holes in active layer and injects asymmetric situation, and the luminous efficiency for avoiding LED is being injected
In the case that electric current increases, quickly reduce instead.
Detailed description of the invention
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing.
Fig. 1 is a kind of structural schematic diagram of gallium nitride based LED epitaxial slice provided in an embodiment of the present invention；
Fig. 2 is a kind of process of the production method of gallium nitride based LED epitaxial slice provided in an embodiment of the present invention
Figure.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention
Formula is described in further detail.
The embodiment of the invention provides a kind of gallium nitride based LED epitaxial slices.Fig. 1 provides for the embodiment of the present invention
A kind of gallium nitride based LED epitaxial slice structural schematic diagram.Referring to Fig. 1, the gallium nitride based LED epitaxial slice
Including substrate 10, n type semiconductor layer 20, active layer 30 and p type semiconductor layer 40, n type semiconductor layer 20, active layer 30 and p-type
Semiconductor layer 40 is sequentially laminated on substrate 10.
In the present embodiment, the material of p type semiconductor layer 40 is using the GaN for adulterating Be.
By using Be as P-type dopant in p type semiconductor layer, the acceptor ionization energy of Be is about the embodiment of the present invention
60meV, the acceptor ionization energy (about 250meV) much smaller than Mg can be more easily compared with use Mg is as P-type dopant
Hole is obtained, hole concentration is improved, improves electrons and holes in active layer and injects asymmetric situation, avoid the hair of LED
Light efficiency quickly reduces instead in the case where Injection Current increases.
Optionally, the doping concentration of Be can be 10 in p type semiconductor layer 4018/cm3~1020/cm3, preferably 1019/
cm3。
Specifically, the thickness of p type semiconductor layer 40 can be 100nm~300nm, such as 200nm, realize that effect is good.
Optionally, as shown in Figure 1, the gallium nitride light-emitting diode epitaxial wafer further includes that layer 100, insert layer can be inserted
100 material is using the Al for adulterating MgxInyGa1-x-y0.3,0 < y < 0.1 of N, 0.1 < x <, the setting of insert layer 100 is in N-type half
Between conductor layer 20 and active layer 30.
By the Al that doping Mg is arranged between n type semiconductor layer and active layerxInyGa1-x-y0.3,0 < of N, 0.1 < x <
Y < 0.1, AlxInyGa1-x-yN matches very well with the piezoelectric polarization that first quantum in active layer is built, and builds first quantum
Energy band be in flat condition, be conducive to limit electronics migration, further promote active layer in electrons and holes symmetrical injection.And
And AlxInyGa1-x-yThe band gap of N is very wide, itself can slow down the rate of electron injection active layer, reduce the probability of electronics leakage,
The final injection for improving hole.In addition, AlxInyGa1-x-yMixed with Mg, the hole provided can consume a part of electronics, subtract N
The electron amount of active layer is injected less, while weakening the built in field of active layer, is conducive to hole injection, increases injection active layer
Number of cavities.In conclusion the Al of Mg is adulterated in setting between n type semiconductor layer and active layerxInyGa1-x-yN, 0.1 < x
0.3,0 < y < 0.1 of < can further improve electrons and holes in active layer and inject asymmetric situation, avoid LED
Luminous efficiency Injection Current increase in the case where, instead quickly reduce.
Preferably, the doping concentration of Mg can be 1/ of the doping concentration of Be in p type semiconductor layer 40 in insert layer 100
200~1/50, such as 1/100, it avoids the number of cavities in insert layer excessive and influences the electron number of recombination luminescence in active layer
Amount.
Specifically, the doping concentration of Mg can be 10 in insert layer 10016/cm3~1018/cm3, such as 1017/cm3, realize effect
Fruit is good.
Optionally, the thickness of insert layer 100 can be 5nm~15nm, such as 10nm.The thinner thickness of insert layer, to extension
The crystal structure and series resistance of piece entirety have little effect.
Optionally, as shown in Figure 1, the gallium nitride light-emitting diode epitaxial wafer can also include electronic barrier layer 51, electronics
The material on barrier layer 51 is using the Al for adulterating MgzGa1-zN, 0.1 < z < 0.6, electronic barrier layer 51 are arranged in active layer 30 and P
Between type semiconductor layer 40.
By the way that electronic barrier layer is arranged between active layer and p type semiconductor layer, can partly be led to avoid electron transition to p-type
Non-radiative recombination is carried out with hole in body layer, reduces the injection efficiency in hole in active layer.And electronic barrier layer is made using Mg
For P-type dopant, a small amount of hole can be provided, is conducive to hole injection active layer.
Specifically, the thickness of electronic barrier layer 51 can be 15nm~80nm, preferably 60nm.
Preferably, as shown in Figure 1, the gallium nitride light-emitting diode epitaxial wafer can also include low temperature P-type layer 52, low temperature P
The material of type layer 52 is using the GaN of doping Be, and the setting of low temperature P-type layer 52 is between active layer 30 and electronic barrier layer 51.
It, can be to avoid the higher life of electronic barrier layer by the way that low temperature P-type layer is arranged between active layer and electronic barrier layer
Long temperature causes the phosphide atom in active layer to be precipitated, and influences the luminous efficiency of light emitting diode.
It is highly preferred that the doping concentration of Be can be with the doping concentration phase of Be in p type semiconductor layer 40 in low temperature P-type layer 52
Together, combined effect is good.
Specifically, the thickness of low temperature P-type layer 52 can be 10nm~50nm, preferably 30nm.
In the present embodiment, the material of substrate 10 can use sapphire (main material is aluminum oxide), such as crystal orientation
For the sapphire of [0001].The material of n type semiconductor layer 20 can use the gallium nitride of n-type doping (such as silicon or germanium).It is active
Layer 30 may include the multiple laminated construction stacked gradually, and each laminated construction includes that the quantum stacked gradually is built and Quantum Well,
To cooperate with insert layer；The material of Quantum Well can use InGaN (InGaN), such as InzGa1-zN, 0 < z < 1, quantum are built
Material can use gallium nitride.
Further, the thickness of n type semiconductor layer 20 can be 1 μm~3 μm, preferably 2 μm；N in n type semiconductor layer 20
The doping concentration of type dopant can be 1018/cm3~1020/cm3, preferably 1019/cm3.The thickness of Quantum Well can be 3nm
~4nm, preferably 3.5nm；The thickness that quantum is built can be 9nm~20nm, preferably 15nm；The quantity and quantum of Quantum Well are built
Quantity it is identical, quantum build quantity can be 6~12, preferably 9.
Optionally, as shown in Figure 1, the gallium nitride based LED epitaxial slice can also include buffer layer 61, buffer layer
61 are arranged between substrate 10 and n type semiconductor layer 20, are answered with alleviate that lattice mismatch between substrate material and gallium nitride generates
Power and defect, and nuclearing centre is provided for gallium nitride material epitaxial growth.
Specifically, the material of buffer layer 61 can use gallium nitride.
Further, the thickness of buffer layer 61 can be 20nm~50nm, preferably 35nm.
Preferably, as shown in Figure 1, the gallium nitride based LED epitaxial slice can also include undoped gallium nitride layer
62, undoped gallium nitride layer 62 is arranged between buffer layer 61 and n type semiconductor layer 20, further to alleviate substrate material and nitrogen
Change the stress and defect that lattice mismatch generates between gallium, provides crystal quality preferable growing surface for epitaxial wafer main structure.
In specific implementation, buffer layer is the gallium nitride of the layer of low-temperature epitaxy first in patterned substrate, because
This is also referred to as low temperature buffer layer.The longitudinal growth for carrying out gallium nitride in low temperature buffer layer again, will form multiple mutually independent three
Island structure is tieed up, referred to as three-dimensional nucleating layer；Then it is carried out between each three-dimensional island structure on all three-dimensional island structures
The cross growth of gallium nitride forms two-dimension plane structure, referred to as two-dimentional retrieving layer；The finally high growth temperature one on two-dimensional growth layer
The thicker gallium nitride of layer, referred to as intrinsic gallium nitride layer.By three-dimensional nucleating layer, two-dimentional retrieving layer and intrinsic gallium nitride in the present embodiment
Layer is referred to as undoped gallium nitride layer.
Further, the thickness of three-dimensional nucleating layer can be 400nm~600nm, preferably 500nm；Two-dimentional retrieving layer
Thickness can be 500nm~800nm, preferably 650nm；The thickness of intrinsic gallium nitride layer can for 1 μm~2 μm, preferably 1.5
μm。
Optionally, as shown in Figure 1, the gallium nitride based LED epitaxial slice can also include contact layer 70, contact layer
70 are arranged on p type semiconductor layer 40, to be formed between the electrode or transparent conductive film that are formed in chip fabrication technique
Ohmic contact.
Specifically, the material of contact layer 90 can be using the InGaN or gallium nitride of p-type doping.
Preferably, the P-type dopant in contact layer 90 can use Be, increase the hole concentration in contact layer, promote electricity
Stream injection, reduces the forward voltage of LED.
Further, the thickness of contact layer 90 can be 5nm~100nm, preferably 50nm；P-type is adulterated in contact layer 90
The doping concentration of agent can be 1021/cm3~1022/cm3, preferably 5*1021/cm3。
The embodiment of the invention provides a kind of production methods of gallium nitride based LED epitaxial slice.Fig. 2 is the present invention
A kind of flow chart of the production method for gallium nitride based LED epitaxial slice that embodiment provides.Referring to fig. 2, the production method
Include:
Step 201: a substrate is provided.
Optionally, which may include:
1 minute~10 minutes (preferably 6 minutes) annealings are carried out to substrate in hydrogen atmosphere；
Controlled at 1000 DEG C~1200 DEG C (preferably 1100 DEG C), nitrogen treatment is carried out to substrate.
The surface for cleaning substrate through the above steps avoids being conducive to the life for improving epitaxial wafer in impurity incorporation epitaxial wafer
Long quality.
Step 202: successively growing n type semiconductor layer, active layer and p type semiconductor layer on substrate.
In the present embodiment, the material of p type semiconductor layer is using the GaN for adulterating Be.
Specifically, which may include:
The first step, controlled at 1050 DEG C~1200 DEG C (preferably 1125 DEG C), pressure is 100torr~500torr
(preferably 300torr), grows n type semiconductor layer on substrate；
Second step grows active layer on n type semiconductor layer；The growth temperature of Quantum Well be 750 DEG C~830 DEG C (preferably
It is 790 DEG C), the growth pressure of Quantum Well is 100torr~500torr (preferably 300torr)；Quantum build growth temperature be
850 DEG C~900 DEG C (preferably 875 DEG C), the growth pressure that quantum is built is 100torr~500torr (preferably 300torr)；
Third step, controlled at 850 DEG C~950 DEG C (preferably 900 DEG C), pressure is that 100torr~300torr is (excellent
It is selected as 200torr), the growing P-type semiconductor layer on active layer.
Optionally, before the first step, which can also include:
Grown buffer layer on substrate.
Correspondingly, n type semiconductor layer is grown on the buffer layer.
Specifically, grown buffer layer on substrate may include:
Controlled at 400 DEG C~600 DEG C (preferably 500 DEG C), pressure be 100torr~300torr (preferably
200torr), grown buffer layer on substrate；
Controlled at 1000 DEG C~1200 DEG C (preferably 1100 DEG C), pressure be 400torr~600torr (preferably
500torr), the in-situ annealing carried out 5 minutes~10 minutes (preferably 8 minutes) to buffer layer is handled.
Preferably, on substrate after grown buffer layer, which can also include:
Undoped gallium nitride layer is grown on the buffer layer.
Correspondingly, n type semiconductor layer is grown on undoped gallium nitride layer.
Specifically, undoped gallium nitride layer is grown on the buffer layer, may include:
Controlled at 1000 DEG C~1080 DEG C (preferably 1040 DEG C), pressure be 250torr~550torr (preferably
400torr), the time is 10 minutes~30 minutes (preferably 20 minutes), on the buffer layer growing three-dimensional nucleating layer；
Controlled at 1050 DEG C~1150 DEG C (preferably 1100 DEG C), pressure be 100torr~500torr (preferably
300torr), the time is 20 minutes~40 minutes (preferably 30 minutes), and two-dimentional retrieving layer is grown on three-dimensional nucleating layer；
Controlled at 1050 DEG C~1200 DEG C (preferably 1125 DEG C), pressure be 100torr~500torr (preferably
300torr), intrinsic gallium nitride layer is grown in two-dimentional retrieving layer.
Optionally, before second step, which can also include:
Insert layer is grown on n type semiconductor layer.
Correspondingly, active layer is grown in insert layer.
Specifically, insert layer is grown on n type semiconductor layer, may include:
Controlled at 750 DEG C~900 DEG C (preferably 825 DEG C), pressure be 100torr~300torr (preferably
200torr), insert layer is grown on n type semiconductor layer；
Stop growing 0.5min~1.5min.
By stopping growing, the memory effect of magnesium is eliminated.
Optionally, before third step, which can also include:
Electronic barrier layer is grown on active layer.
Correspondingly, p type semiconductor layer is grown on electronic barrier layer.
Specifically, electronic barrier layer is grown on active layer, may include:
Controlled at 900 DEG C~1000 DEG C (preferably 950 DEG C), pressure be 100torr~500torr (preferably
300torr), electronic barrier layer is grown on active layer.
Preferably, before growing electronic barrier layer on active layer, which can also include:
The growing low temperature P-type layer on active layer.
Correspondingly, electronic barrier layer is grown in low temperature P-type layer.
Specifically, the growing low temperature P-type layer on active layer may include:
Controlled at 600 DEG C~850 DEG C (preferably 750 DEG C), pressure be 100torr~600torr (preferably
300torr), the growing low temperature P-type layer on active layer.
Optionally, after third step, which can also include:
Contact layer is grown on p type semiconductor layer.
Specifically, contact layer is grown on p type semiconductor layer, may include:
Controlled at 850 DEG C~1000 DEG C (preferably 925 DEG C), pressure be 100torr~300torr (preferably
200torr), contact layer is grown on p type semiconductor layer.
It should be noted that after above-mentioned epitaxial growth terminates, can first by temperature be reduced to 650 DEG C~850 DEG C (preferably
It is 750 DEG C), the annealing of 5 minutes~15 minutes (preferably 10 minutes) is carried out to epitaxial wafer in nitrogen atmosphere, then again
The temperature of epitaxial wafer is reduced to room temperature.
Control temperature, pressure each mean temperature, pressure in the reaction chamber of control growth epitaxial wafer, and specially metal is organic
Compound chemical gaseous phase deposition (English: Metal-organic Chemical Vapor Deposition, referred to as: MOCVD) set
Standby reaction chamber.Using trimethyl gallium or triethyl-gallium as gallium source when realization, high-purity ammonia is as nitrogen source, and trimethyl indium is as indium
Source, trimethyl aluminium is as silicon source, and silane is as silicon source, and tetramethyl germanium is as ge source, and two luxuriant magnesium are as magnesium source.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of gallium nitride based LED epitaxial slice, the gallium nitride based LED epitaxial slice includes substrate, N-type half
Conductor layer, active layer and p type semiconductor layer, the n type semiconductor layer, the active layer and the p type semiconductor layer successively layer
It folds over the substrate, which is characterized in that the material of the p type semiconductor layer is using the GaN for adulterating Be.
2. gallium nitride based LED epitaxial slice according to claim 1, which is characterized in that the p type semiconductor layer
The doping concentration of middle Be is 1018/cm3~1020/cm3。
3. gallium nitride based LED epitaxial slice according to claim 1 or 2, which is characterized in that the gallium nitride hair
Optical diode epitaxial wafer further includes insert layer, and the material of the insert layer is using the Al for adulterating MgxInyGa1-x-yN, 0.1 < x <
0.3,0 < y < 0.1, the insert layer are arranged between the n type semiconductor layer and the active layer.
4. gallium nitride based LED epitaxial slice according to claim 3, which is characterized in that Mg in the insert layer
Doping concentration is 1/200~1/50 of the doping concentration of Be in the p type semiconductor layer.
5. gallium nitride based LED epitaxial slice according to claim 4, which is characterized in that Mg in the insert layer
Doping concentration is 1016/cm3~1018/cm3。
6. gallium nitride based LED epitaxial slice according to claim 3, which is characterized in that the thickness of the insert layer
For 5nm~15nm.
7. gallium nitride based LED epitaxial slice according to claim 1 or 2, which is characterized in that the gallium nitride hair
Optical diode epitaxial wafer further includes electronic barrier layer, and the material of the electronic barrier layer is using the Al for adulterating MgzGa1-zN, 0.1 <
Z < 0.6, the electronic barrier layer are arranged between the active layer and the p type semiconductor layer.
8. gallium nitride based LED epitaxial slice according to claim 7, which is characterized in that the gallium nitride light-emitting two
Pole pipe epitaxial wafer further includes low temperature P-type layer, and using the GaN for adulterating Be, the low temperature P-type layer is set the material of the low temperature P-type layer
It sets between the active layer and the electronic barrier layer.
9. gallium nitride based LED epitaxial slice according to claim 8, which is characterized in that in the low temperature P-type layer
The doping concentration of Be is identical as the doping concentration of Be in the p type semiconductor layer.
10. a kind of production method of gallium nitride based LED epitaxial slice, which is characterized in that the production method includes:
One substrate is provided；
N type semiconductor layer, active layer and p type semiconductor layer are successively grown over the substrate；
Wherein, the material of the p type semiconductor layer is using the GaN for adulterating Be.
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