CN103579425A - Gallium nitride series light-emitting diode and manufacturing method - Google Patents
Gallium nitride series light-emitting diode and manufacturing method Download PDFInfo
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- CN103579425A CN103579425A CN201310566095.9A CN201310566095A CN103579425A CN 103579425 A CN103579425 A CN 103579425A CN 201310566095 A CN201310566095 A CN 201310566095A CN 103579425 A CN103579425 A CN 103579425A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L33/005—Processes
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L33/02—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 characterised by the semiconductor bodies
- H01L33/12—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 characterised by the semiconductor bodies with a stress relaxation structure, e.g. buffer layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L33/02—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 characterised by the semiconductor bodies
- H01L33/14—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 characterised by the semiconductor bodies with a carrier transport control structure, e.g. highly-doped semiconductor layer or current-blocking structure
- H01L33/145—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 characterised by the semiconductor bodies with a carrier transport control structure, e.g. highly-doped semiconductor layer or current-blocking structure with a current-blocking structure
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Abstract
The invention discloses a gallium nitride series light-emitting diode and a manufacturing method. The gallium nitride series light-emitting diode comprises a substrate, a gallium nitride nucleating layer, a buffering layer, an n-type contact layer, an activity light-emitting layer, a p-type electron barrier layer, a p-type contact layer, a negative electrode and a positive electrode, wherein the gallium nitride nucleating layer is manufactured on the substrate, the buffering layer is manufactured on the gallium nitride nucleating layer, the n-type contact layer is manufactured on the buffering layer, a table top is arranged on one side of the upper face of the n-type contact layer, the activity light-emitting layer is manufactured on the n-type contact layer and covers the surface, except for the table top, of the n-type contact layer, the p-type electron barrier layer is manufactured on the activity light-emitting layer, the lower surface of the p-type electron barrier layer is in contact with an aluminum indium gallium nitrogen thin layer, the p-type contact layer is grown on the p-type electron barrier layer, the negative electrode is manufactured on the table top of one side of the n-type contact layer, and the positive electrode is manufactured on the p-type contact layer. According to the gallium nitride series light-emitting diode and the manufacturing method, introduction of a donor functional group can be reduced, the doping efficiency of magnesium can be improved, and therefore the hole concentration of p-type gallium nitride can be improved.
Description
Technical field
The present invention relates to a kind of gallium nitride (GaN) series LED, particularly relate to a kind of GaN series LED and preparation method.
Background technology
III-V family photoelectric semiconductor material is described as third generation semi-conducting material at present.And GaN series LED owing to producing the light-emitting diode (referred to as " LED ") of various coloured light (blue light or the purple light that especially need high energy gap) by controlling the composition of material, and becomes the emphasis of industry research.
The epitaxial growth that the GaN of take is basic semi-conducting material or device is the main MOCVD technology that adopts at present.In utilizing the technique of MOCVD technology growth nitride-based semiconductor (GaN, AlN, InN and their alloy nitride), p-type doping techniques is the key technology of efficient GaN base photoelectric device research, is also the important content of studying at present.The height of p-type doping content will directly affect ohmic contact quality and the device performance of GaN base photoelectric device, p-type Effective Doping concentration is too low will cause p-type ohmic contact preparation difficulty, thereby can reduce the injection ratio of pn knot, reduce luminous efficiency, increase device forward operating voltage, make device heating, cannot meet high-power light-emitting requirement.
In GaN, typical acceptor impurity is magnesium (Mg), belongs to deep acceptor impurity.The difficult point of p-type doping (as low in solid solubility, ionization energy is high) originates from the one-tenth bond structure of Mg in GaN crystal after all, and the valence band structure that determines of this one-tenth key form.Although it is lower, still too high that the activation energy of Mg (about 215meV) and other acceptor compare genus, even the doping content of Mg reaches 1 * 10 under room temperature
20cm
-3, also only have about 1% Mg ionization.In addition, Mg also can with material in H form complex compound Mg-H (being hydrogen passivation), the hole concentration of p-type GaN is further reduced, so the hole concentration of p-type GaN is all difficult to reach 1 * 10 conventionally at present
18cm
-3, mostly in 3-7 * 10
17cm
-3scope, effective, controlled high concentration p-type doping techniques is the technical bottleneck of restriction GaN sill and device development always.The present invention relates to p-type GaN growing method--the growing method of pulse, rich nitrogen of the efficient doping of a kind of Mg.The physical mechanism of the method is: on the one hand because Mg can be negative value in the formation of growing surface, easy enrichment also enters lattice, and growth course adopts pulsed epitaxy technique; On the other hand, because Mg substitutes Ga atom in growth course, enter GaN lattice, so in growth course, more N dangling bonds are more conducive to the combination of Mg than Ga dangling bonds.
Summary of the invention
The object of the present invention is to provide a kind of GaN series LED and preparation method, it is the introducing that can roll into a ball in order to reduce alms giver's base, improves the doping efficiency of magnesium, thereby increases the hole concentration of p-type gallium nitride.
The invention provides a kind of GaN series LED, it comprises:
One substrate;
One gallium nitride nucleating layer, this gallium nitride nucleating layer is produced on substrate;
One resilient coating, this resilient coating is produced on nucleating layer;
One N-shaped contact layer, this N-shaped contact layer is produced on resilient coating, and this side above N-shaped contact layer has a table top;
One active luminescent layer, this activity luminescent layer is produced on N-shaped contact layer and covers described N-shaped contact layer table top part surface in addition;
One p-type electronic barrier layer, this p-type electronic barrier layer is produced on active luminescent layer, and its lower surface contacts with aluminium indium gallium nitrogen thin layer;
One p-type contact layer, this p-type contact layer is grown on p-type electronic barrier layer;
One negative electrode, this negative electrode is produced on the table top of N-shaped contact layer one side;
One positive electrode, this positive electrode is produced on p-type contact layer.
The present invention also provides a kind of preparation method of GaN series LED, and it comprises the steps:
Step 1: growing gallium nitride nucleating layer, resilient coating and N-shaped contact layer successively on a substrate, the material of this N-shaped contact layer is N-shaped gallium nitride;
Step 2: at the active luminescent layer of superficial growth one of N-shaped contact layer, this activity luminescent layer is the multiply periodic quantum well structure that indium gallium nitrogen thin layer and aluminium indium gallium nitrogen thin layer interaction cascading form, and periodicity is 5-20:
Step 3: growing p-type electronic barrier layer and p-type contact layer on active luminescent layer, the material of this p-type electronic barrier layer is aluminium indium gallium nitrogen, the material of this p-type contact layer is p-type gallium nitride;
Step 4: adopt the method for etching, etch into N-shaped contact layer from epi-layer surface, and the side on N-shaped contact layer forms a table top always;
Step 5: make a negative electrode on the table top of N-shaped contact layer one side;
Step 6: make a positive electrode on p-type contact layer, complete preparation.
Accompanying drawing explanation
For further illustrating technology contents of the present invention, below in conjunction with the drawings and specific embodiments, the present invention will be described in more detail, wherein:
Fig. 1 is the structural representation of GaN series LED of the present invention.
Fig. 2 is preparation flow figure of the present invention.
Fig. 3 is GaN series LED growth schematic diagram of the present invention.
Embodiment
Refer to shown in Fig. 1, the invention provides a kind of GaN series LED, it comprises:
One substrate 11, with (0001) to sapphire (Al
2o
3) be substrate, other materials that can be used for substrate 11 also comprise that alumina single crystal, 6H-SiC, 4H-SiC, Si monocrystalline or the lattice constant of R-face or A-face are close to the monocrystalline oxide of nitride-based semiconductor.In preparation, adopt high-purity N H
3do N source, high-purity H
2and N
2mist do carrier gas; Trimethyl gallium (TMGa) or triethyl-gallium are done Ga source, and trimethyl indium (TMIn) is done In source, and trimethyl aluminium (TMAl) is done Al source; N-shaped dopant is silane (SiH
4), p-type dopant is two luxuriant magnesium (CP
2mg);
One gallium nitride nucleating layer 12, this gallium nitride nucleating layer 12 is produced on substrate 11.Growth parameter(s) comprises: 500 ℃ to 800 ℃ of reaction temperatures, and reaction chamber pressure 200 is to 500Torr, carrier gas flux 10-30 liter/min, TMGa flow rate 20-250 micromole/minute, ammonia flow 20-80 moles/min, growth time 1-10 minute;
One resilient coating 13, this resilient coating 13 is produced on nucleating layer 12, and this resilient coating 13 consists of gallium nitride.Growth parameter(s) comprises: 9501180 ℃ of reaction temperatures, reaction chamber pressure 76-760Torr, carrier gas flux 5-20 liter/min, TMGa flow rate be 80-400 micromole/minute, ammonia flow is 200800 moles/min, growth time 20-60 minute;
One N-shaped contact layer 14, this N-shaped contact layer 14 is produced on resilient coating 13, and this N-shaped contact layer 14 side above has a table top 141, and this N-shaped contact layer 14 consists of N-shaped gallium nitride.Growth parameter(s) comprises: reaction temperature 950-1150 ℃, reaction chamber pressure 76-760Torr, carrier gas flux 5-20 liter/min, TMGa flow rate 80-400 micromole/minute, ammonia flow 200-800 moles/min, silane flow rate 0.2-2.0 nanomole/minute, growth time 10-40 minute;
One active luminescent layer 15, this activity luminescent layer 15 is produced on N-shaped contact layer 14 and covers the part surface of described N-shaped contact layer 14, and described active luminescent layer 15 is that the multiply periodic quantum well structure being formed by indium gallium nitrogen (InGaN) thin layer 151 and aluminium indium gallium nitrogen (AlIn6aN) thin layer 152 interaction cascadings forms.Growth parameter(s) comprises: AlInGaN thin layer (building layer 152): reaction temperature 700-900 ℃, reaction chamber pressure 100-500Torr, carrier gas flux 5-20 liter/min, ammonia flow 200-800 moles/min, trimethyl indium flow 10-50 micromole/minute, TMGa flow rate 0.1-1.0 micromole/minute, trimethyl aluminium flow 20-100 micromole/minute, silane flow rate 0-2.0 nanomole/minute, time 0.1-5 minute; InGaN thin layer (being trap layer 151): reaction temperature 700-850 ℃, reaction chamber pressure 100-500Torr, carrier gas flux 5-20 liter/min, ammonia flow 200-800 moles/min, TMGa flow rate 0.1-1.0 micromole/minute, trimethyl indium flow 10-50 micromole/minute, time 0.1-5 minute; Multiple Quantum Well periodicity is 5-20;
One p-type electronic barrier layer 16, this p-type electronic barrier layer 16 is produced on active luminescent layer 15, and this p-type electronic barrier layer 16 consists of aluminium indium gallium nitrogen.The thickness of described p-type electronic barrier layer 16 is 10-50nm, and the lower surface of described p-type electronic barrier layer contacts with the aluminium indium gallium nitrogen thin layer 152 in described active luminescent layer.Growth parameter(s) comprises: reaction temperature 700-1000 ℃, reaction chamber pressure 50-200Torr, carrier gas flux 5-20 liter/min, ammonia flow 100-400 moles/min, trimethyl indium flow 10-50 micromole/minute, trimethyl aluminium flow 20-100 micromole/minute, TMGa flow rate 80-200 micromole/minute, two luxuriant magnesium flows be 150-400 nanomole/minute, time 1-10 minute.
Wherein said p-type electronic barrier layer 16 be take two luxuriant magnesium as p-type dopant, and the doping content of two luxuriant magnesium is 10
19-10
21cm
-3.
One p-type contact layer 17, this p-type contact layer 17 is produced on p-type electronic barrier layer 16, and this p-type contact layer 17 consists of p-type gallium nitride, and thickness is 50-300 nanometer.Growth parameter(s) comprises: reaction temperature 950-1100 ℃, reaction chamber pressure 200-500Torr, carrier gas flux 5-20 liter/min, ammonia flow 200-800 moles/min, TMGa flow rate 80-400 micromole/minute, two luxuriant magnesium flows be 0.5-5 micromole/minute.
Wherein said p-type contact layer 17 adopts the method growth of pulse, rich nitrogen.
One negative electrode 18, this negative electrode 18 is produced on the table top 141 of N-shaped contact layer 14 1 sides, chromium platinum or titanium aluminium titanium, consists of.
One positive electrode 19, this positive electrode 19 is produced on p-type contact layer 17, chromium platinum, consists of.
Refer to shown in Fig. 2 and in conjunction with consulting Fig. 1, the invention provides a kind of preparation method of GaN series LED, it comprises the steps:
Step 1: growing gallium nitride nucleating layer 12, resilient coating 13 and N-shaped contact layer 14 successively on a substrate 11, the material of this N-shaped contact layer 14 is N-shaped gallium nitride;
Step 2: at the active luminescent layer 15 of superficial growth one of N-shaped contact layer 14, this activity luminescent layer 15 is multiply periodic quantum well structures that indium gallium nitrogen thin layer 151 and aluminium indium gallium nitrogen thin layer 152 interaction cascadings form, and periodicity is 5-20;
Step 3: growing p-type electronic barrier layer 16 and p-type contact layer 17 on active luminescent layer 15, the material of this p-type electronic barrier layer 16 is aluminium indium gallium nitrogen, the material of this p-type contact layer 17 is p-type gallium nitride, this p-type contact layer 17 is grown under the condition of pulse, rich nitrogen, and this growth is to adopt the pulsed switching in gallium source to realize.The material of this p-type contact layer 17 is that p-type gallium nitride thickness is 50-300 nanometer, and the growth temperature of described p-type contact layer 17 is 800-1100 ℃, and growth pressure is 50-760torr, and described p-type contact layer 17 is with H
2or H
2with N
2mist do carrier gas;
Step 4: adopt the method for etching, etch into N-shaped contact layer 14 from epi-layer surface, and the side on N-shaped contact layer 14 forms a table top 141 always;
Step 5: make a negative electrode 18 on the table top 141 of N-shaped contact layer 14 1 sides;
Step 6: make a positive electrode 19 on p-type contact layer 17, complete preparation.
Wherein said p-type contact layer 17 adopts the method growth of pulse, rich nitrogen.Concrete growth course as shown in Figure 3.
At early growth period, open gallium source 5-360 second, keep NH
3for passing into state, two luxuriant magnesium dopants can pass into also and can not pass into;
Close gallium source 5-360 second, keep NH
3for passing into state, pass into two luxuriant magnesium dopants simultaneously;
Repeat aforementioned two steps, until the thickness of described p-type contact layer 17 is 50-300 nanometer.Complete the making of p-type contact layer 17.
The above; be only the embodiment in the present invention, but protection scope of the present invention is not limited to this, any people who is familiar with this technology is in the disclosed technical scope of the present invention; the conversion that can expect easily or replacement, all should be encompassed in of the present invention comprise scope within.Therefore, protection scope of the present invention should be as the criterion with the protection range of claims.
Claims (10)
1. a GaN series LED, it comprises:
One substrate;
One gallium nitride nucleating layer, this gallium nitride nucleating layer is produced on substrate;
One resilient coating, this resilient coating is produced on nucleating layer;
One N-shaped contact layer, this N-shaped contact layer is produced on resilient coating, and this side above N-shaped contact layer has a table top;
One active luminescent layer, this activity luminescent layer is produced on N-shaped contact layer and covers described N-shaped contact layer table top part surface in addition;
One p-type electronic barrier layer, this p-type electronic barrier layer is produced on active luminescent layer, and its lower surface contacts with aluminium indium gallium nitrogen thin layer;
One p-type contact layer, this p-type contact layer is grown on p-type electronic barrier layer;
One negative electrode, this negative electrode is produced on the table top of N-shaped contact layer one side;
One positive electrode, this positive electrode is produced on p-type contact layer.
2. GaN series LED as claimed in claim 1, wherein the material of this N-shaped contact layer is N-shaped gallium nitride.
3. GaN series LED as claimed in claim 1, wherein said active luminescent layer is the multiply periodic quantum well structure that indium gallium nitrogen thin layer and aluminium indium gallium nitrogen thin layer interaction cascading form, periodicity is 5-20.
4. GaN series LED as claimed in claim 1, wherein the material of this p-type electronic barrier layer is aluminium indium gallium nitrogen.
5. GaN series LED as claimed in claim 1, wherein the material of this p-type contact layer is p-type gallium nitride, thickness is 50-300 nanometer.
6. a preparation method for GaN series LED, it comprises the steps:
Step 1: growing gallium nitride nucleating layer, resilient coating and N-shaped contact layer successively on a substrate, the material of this N-shaped contact layer is N-shaped gallium nitride;
Step 2: at the active luminescent layer of superficial growth one of N-shaped contact layer, this activity luminescent layer is the multiply periodic quantum well structure that indium gallium nitrogen thin layer and aluminium indium gallium nitrogen thin layer interaction cascading form, and periodicity is 5-20;
Step 3: growing p-type electronic barrier layer and p-type contact layer on active luminescent layer, the material of this p-type electronic barrier layer is aluminium indium gallium nitrogen, the material of this p-type contact layer is p-type gallium nitride;
Step 4: adopt the method for etching, etch into N-shaped contact layer from epi-layer surface, and the side on N-shaped contact layer forms a table top always;
Step 5: make a negative electrode on the table top of N-shaped contact layer one side;
Step 6: make a positive electrode on p-type contact layer, complete preparation.
7. the preparation method of GaN series LED as claimed in claim 7, wherein the material of this p-type contact layer is that p-type gallium nitride thickness is 50-300 nanometer.
8. the preparation method of GaN series LED as claimed in claim 7, wherein this p-type contact layer is grown under the condition of pulse, rich nitrogen, this growth is to adopt the pulsed switching in gallium source to realize, all the time to pass into the time of closing gallium source be 5-360 second to ammonia therebetween, the time of opening gallium source is 5-360 second, and described p-type contact layer is with H
2or H
2with N
2mist do carrier gas.
9. the preparation method of GaN series LED as claimed in claim 8, passes into the time of opening in ，Jia source, magnesium source to pass into magnesium source or do not pass into magnesium source in the time that wherein gallium source is closed.
10. the preparation method of GaN series LED as claimed in claim 7, wherein the growth temperature of p-type contact layer is 800-1100 ℃, growth pressure is 50-760torr.
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Cited By (3)
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| CN105280768A (en) * | 2015-09-18 | 2016-01-27 | 华灿光电股份有限公司 | Epitaxial wafer growth method having high luminescence efficiency |
| CN109326698A (en) * | 2018-09-27 | 2019-02-12 | 华灿光电（浙江）有限公司 | A kind of manufacturing method of LED epitaxial slice |
| CN112768570A (en) * | 2020-12-31 | 2021-05-07 | 华灿光电（浙江）有限公司 | Method for manufacturing gallium nitride-based light emitting diode epitaxial wafer |
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| CN102185052A (en) * | 2011-05-05 | 2011-09-14 | 中国科学院半导体研究所 | Manufacturing method of modulation-doped gallium nitride series light-emitting diode |
| CN103367594A (en) * | 2013-07-26 | 2013-10-23 | 东南大学 | Light emitting diode and preparation method thereof |
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| CN105280768A (en) * | 2015-09-18 | 2016-01-27 | 华灿光电股份有限公司 | Epitaxial wafer growth method having high luminescence efficiency |
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Application publication date: 20140212 |