CN105762248B - A kind of light emitting diode and preparation method thereof - Google Patents

A kind of light emitting diode and preparation method thereof Download PDF

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Publication number
CN105762248B
CN105762248B CN201610320407.1A CN201610320407A CN105762248B CN 105762248 B CN105762248 B CN 105762248B CN 201610320407 A CN201610320407 A CN 201610320407A CN 105762248 B CN105762248 B CN 105762248B
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layer
indium
type
magnesium
emitting diode
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CN105762248A (en
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黄文宾
蔡吉明
黄静
林兓兓
张家宏
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Anhui Sanan Optoelectronics Co Ltd
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Anhui Sanan Optoelectronics Co Ltd
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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
    • 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
    • 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
    • H01L33/26—Materials of the light emitting region
    • H01L33/30—Materials of the light emitting region containing only elements of group III and group V of the periodic system
    • H01L33/32—Materials of the light emitting region containing only elements of group III and group V of the periodic system containing nitrogen

Abstract

The invention belongs to technical field of semiconductors, more particularly to a kind of light emitting diode and preparation method thereof, indium enriched layer is formed in active layer surface first, in favor of the deposition of subsequent nitridation indium；Grow up to form the p-type insert layer of magnesium Delta doping by substep, low temperature afterwards, the p-type insert layer includes indium enriched layer, the first nitride indium layer, magnesium enriched layer and the second nitride indium layer, since the energy gap for nitrogenizing phosphide material is relatively low, magnesium source is set to diffuse into the first nitride indium layer and the second nitride indium layer using moment high magnesium density, add the efficiency of p-type insert layer incorporation magnesium, and then increase the hole concentration of magnesium and reduce the activation energy of magnesium, the position in p n junctions area is adjusted, lifts the Internal Quantum luminous efficiency of device；The nitride indium layer of low-temperature epitaxy can reduce the destruction to active layer at the same time.

Description

A kind of light emitting diode and preparation method thereof
Technical field
The invention belongs to technical field of semiconductors, more particularly to a kind of light emitting diode and preparation method thereof.
Background technology
Light emitting diode（Light-emitting diode, LED）It is a kind of injection lelctroluminescence device, in energy saving and intelligence Energy control aspect is received significant attention and applied.The particularly LED of GaN base material, since its wavelength covers whole visible ray Wave band and ultraviolet band, and as the main flow direction of current LED development.Therefore how to improve the injection efficiency of carrier and then carry The luminescent properties of high LED are the hot spots of those skilled in the art's research.
Existing P-type layer generally comprises p-type AlGaN electronic barrier layers, high temperature p-type GaN layer and p-type contact layer, but due to P The activation of magnesium can be higher in type AlGaN and p-type GaN contact layers（General P-AlGaN is 215meV, p-GaN 175meV）, room temperature Only have a small amount of magnesium to be activated down, hole concentration is very low.Caused by direct result be that p-n junction junction region location largely falls in p-type In area, and active light-emitting layer is because barrier layer is doped to n-type area, and only a small amount of Quantum Well, which is located in p-n junction area, to be participated in shining, therefore Luminous intensity is weaker.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of light emitting diode, including at least the N-type stacked gradually Layer, active layer and P-type layer, it is characterised in that：A p-type insert layer is further included between the P-type layer and be set forth in active layer, it is described P-type insert layer includes indium enriched layer, the first nitride indium layer, magnesium enriched layer and the second nitride indium layer of periodically stacking.
Preferably, a transition zone is further included between the p-type insert layer and the P-type layer.
Preferably, the transition zone is AlxInyGa1-x-yN layers, wherein, 0≤x<1,0≤y<1,0≤x+y<1.
Present invention also offers a kind of method of light emitting diode, including at least following steps：
Prepare N-type layer；
In preparing active layer in the N-type layer；
In preparing P-type layer on the active layer；
It is characterized in that：The step of preparing p-type insert layer is further included before the preparation P-type layer, is specially：
1) reduces reaction chamber temperature, closes nitrogen source, is passed through indium source, and indium enriched layer is formed in active layer surface, in favor of The deposition of subsequent nitridation indium layer；
2) is passed through nitrogen source, forms the first nitride indium layer；
3) closes indium source, is passed through magnesium source；
4) continues to be passed through indium source after closing magnesium source, forms the second nitride indium layer；
5) repeats the above steps 1) -4), form p-type insert layer.
Preferably, the temperature difference of the growth temperature of the growth temperature of the indium enriched layer and first nitride indium layer for 0 ~ 50℃。
Preferably, the growth temperature of second nitride indium layer is greater than or equal to first nitride indium layer, its temperature difference For 0 ~ 50 DEG C.
Preferably, the growth temperature of the p-type insert layer is 400 ~ 800 DEG C.
Preferably, the growth step that the p-type insert layer further includes one transition zone of deposition afterwards is deposited.
Preferably, the transition zone is AlxInyGa1-x-yN material layers, wherein, 0≤x<1,0≤y<1,0≤x+y<1.
Preferably, the step 1) -4) number of repetition be 1 ~ 10 time.
Preferably, the nitrogen source, indium source, magnesium source are respectively by ammonia or nitrogen, trimethyl indium or triethylindium, two luxuriant magnesium There is provided.
The present invention at least has the advantages that：The present invention forms indium enriched layer prior to active layer surface, in favor of rear The deposition of continuous indium nitride；Since the energy gap for nitrogenizing phosphide material is relatively low, magnesium source is set to diffuse into the first nitrogen using moment high magnesium density Change indium layer and the second nitride indium layer, add the efficiency of the first nitride indium layer and the second nitride indium layer incorporation magnesium, and then increase p-type Hole concentration in insert layer, simultaneously as indium nitride energy gap（About 0.67eV）Than gallium nitride energy gap（About 3.4eV）It is small, drop The activation energy of low magnesium, the opposite migration rate for lifting hole, and then the position in p-n junction interface is adjusted, lift the inside amount of device Sub- luminous efficiency；In addition, the nitride indium layer of low-temperature epitaxy can reduce the destruction to active layer.
Brief description of the drawings
Attached drawing is used for providing a further understanding of the present invention, and a part for constitution instruction, the reality with the present invention Apply example to be used to explain the present invention together, be not construed as limiting the invention.
Fig. 1 is the light emitting diode construction schematic diagram of the specific embodiment of the invention 1.
Fig. 2 is the p-type insert layer structure diagram of the specific embodiment of the invention 1.
Fig. 3 is the light emitting diode preparation method flow chart of the specific embodiment of the invention 1；
Fig. 4 is the p-type insert layer preparation method flow chart of the specific embodiment of the invention 1；
Fig. 5 is the light emitting diode preparation method flow chart of the specific embodiment of the invention 2.
Fig. 6 is the light emitting diode construction schematic diagram of the specific embodiment of the invention 2.
Attached drawing marks：100：N-type layer；200：Active layer；300：P-type layer；310：P-type electron barrier layer；320：High temperature P- GaN layer；330：P-type contact layer.400：P-type insert layer；410：Indium enriched layer；420：First nitride indium layer；430：Magnesium enriched layer； 440：Second nitride indium layer；500：Transition zone.
Embodiment
The embodiment of the present invention is described in detail below in conjunction with attached drawing, but the present invention can be limited according to claim Fixed and covering multitude of different ways is implemented.
Embodiment 1
Referring to attached drawing 1, a kind of light emitting diode provided by the invention, including at least the N-type layer 100, active stacked gradually Layer 200 and P-type layer 300, wherein, P-type layer 300 includes P-type electron barrier layer 310, high temperature P-GaN layers 320 and the P stacked gradually Type contact layer 330.N-type impurity is any one in silicon, germanium, tin, for providing electronics；P type impurity for beryllium, magnesium, calcium, strontium, Any one in barium, for providing hole.P-type electron barrier layer 310 is p-type AlGaN material, and active layer 200 is by InGaN The periodic structure of well layer and GaN barrier layer composition, its periodicity are 4 ~ 12.Since the mobility (Mobility) of electronics compares hole It is 10 times high（Electron mobility>1500cm2/ vs, hole<200cm2/vs）, therefore to reduce the migration rate of electronics, adjust p-type Al components stop electronics overflow in N-type layer 100 in electronic barrier layer 310.330 material of p-type contact layer is GaN, its thickness is 10 ~ 100, its p type impurity concentration is 1 × 1019~1×1022 cm-3。
The light emitting diode of the present invention further includes the p-type insertion between active layer 200 and P-type electron barrier layer 310 Layer 400, referring to attached drawing 2, it is rich that p-type insert layer 400 includes periodically the indium enriched layer 410 of stacking, the first nitride indium layer 420, magnesium Collect 430 and second nitride indium layer 440 of layer, its stacking periods number is 1 ~ 10 time.Magnesium enriched layer 430 forms moment high magnesium density, And by the diffusion effect and memory effect of magnesium, make to form magnesium Delta in the first nitride indium layer 420 and the second nitride indium layer 440 Doping, increases the injection efficiency of magnesium, and then increases the hole concentration in p-type insert layer 400 and reduce the activation energy of magnesium；Meanwhile Reduce hole to N-type layer 100 inject when potential barrier height so that the migration rate relative increase in hole, electron-hole are effective Recombination radiation interface is migrated to N-type layer 100, lifts the Internal Quantum luminous efficiency of device.
Referring to attached drawing 3 ~ 4, present invention also offers a kind of light-emitting diodes tube preparation method, including at least following steps：System Standby N-type layer 100；Prepare active layer 200；P-type layer 300 is prepared, wherein P-type layer 300 includes growing P-type electronic barrier layer successively 310th, the step of high temperature P-GaN layers 320, p-type contact layer 330；Further to prevent electronics overflow and increasing the injection effect in hole Rate, present invention additionally comprises between active layer 200 and P-type electron barrier layer 310 the step of growing P-type insert layer 400, specifically For：
1) reduces reaction chamber temperature, closes nitrogen source, is passed through indium source, and indium enriched layer 410 is formed in 200 surface of active layer, In favor of the deposition of follow-up first nitride indium layer, 420 and second nitride indium layer 440；
2) is passed through nitrogen source, forms the first nitride indium layer 420；
3) closes indium source and nitrogen source, is passed through magnesium source, forms magnesium enriched layer 430；
4) continues to be passed through indium source and nitrogen source after closing magnesium source, forms the second nitride indium layer 440；
5) repeats the above steps 1) -4) 1 ~ 10 time, form p-type insert layer 400.
Wherein, nitrogen source, indium source, magnesium source are provided by ammonia or nitrogen, trimethyl indium or triethylindium, two luxuriant magnesium respectively. The p-type insert layer 400 of magnesium Delta doping is formed by substep, spreads magnesium source with the magnesium enriched layer 430 of moment high magnesium density Into the first nitride indium layer 420 and the second nitride indium layer 440, add the first nitride indium layer 420 and the second nitride indium layer 440 is mixed Enter the efficiency of magnesium, and then increase the hole concentration of magnesium in P-type layer 300, reduce it and activate energy.On the other hand, due to indium nitride material The energy gap of material is relatively low（About 0.7eV）, the height for the potential barrier that hole is injected to N-type layer 100 is reduced, increases hole injection efficiency, The position in p-n junction interface is adjusted, effective recombination radiation probability of electron-hole is improved.
Meanwhile nitrogenize phosphide material there is the characteristic that easily separates out of high temperature, therefore, the temperature range of p-type insert layer 400 for 400 ~ 800 DEG C, the excessive formation for being unfavorable for indium nitride of temperature, while also its crystal quality is destroyed because of the baking to active layer 200.The One nitride indium layer 420 is identical or different from the growth time of the second nitride indium layer 440；The growth temperature of indium enriched layer 410 with The temperature difference of the growth temperature of first nitride indium layer 420 is 0 ~ 50 DEG C.The indium enriched layer 410 of low temperature growth is the first nitride indium layer 420 deposition provides growth basic point, obtains the first nitride indium layer 420 of better quality, and its growth temperature is 400 ~ 600 DEG C.Magnesium The growth temperature of enriched layer 430 is greater than or equal to first nitride indium layer 420, its temperature difference is 0 ~ 50 DEG C, relatively low growth Temperature is not easy to the fracture of Mg-H keys, and the activation efficiency of magnesium is relatively low；The growth temperature of same second nitride indium layer 440 is higher than or waits In 420 growth temperature of the first nitride indium layer, poor temperature difference is 0 ~ 50 DEG C, and the second nitride indium layer 440 of higher temperature growth rises Acted on to temperature transition, to be easy to the growth of subsequent high temperature P-type layer 300, prevent instantaneous high-temperature to 400 lattice of p-type insert layer Destroy.
Embodiment 2
Referring to attached drawing 5, difference lies between growing P-type insert layer 400 and P-type layer 300 with embodiment 1 by the present invention It is Al to further include one material of growthxInyGa1-x-yThe step of transition zone 500 of N, hindered with reducing p-type insert layer 400 with p-type electronics Polarity effect caused by lattice mismatch between barrier 310, its growth temperature is between p-type insert layer 400 and P-type electron barrier layer Between 310, play the role of temperature transition, transition zone AlxInyGa1-x-yN material layers, 0≤x<1,0≤y<1,0≤x+y<1.And Indium source enriched layer 410, the first nitride indium layer 420,430 and second nitride indium layer 440 of magnesium enriched layer in the p-type insert layer 400 Growth temperature it is identical, and the first nitride indium layer 420 is identical with the growth time of the second nitride indium layer 440, is 10 ~ 60 seconds. Other growth conditions and beneficial effect are identical with described in embodiment 1, are not stated herein tired.
A kind of light emitting diode provided in this embodiment, referring to attached drawing 6, includes at least successively：N-type layer 100, active layer 200th, P-type layer 300, and p-type insert layer 400 and transition zone 500 between active layer 200 and P-type layer 300, wherein, p-type Insert layer 400 includes periodically the indium enriched layer 410 of stacking, the first nitride indium layer 420,430 and second indium nitride of magnesium enriched layer Layer 440, its periodicity stacking times are 1 ~ 10 time；Transition zone 500 plays crystalline substance between p-type insert layer 400 and P-type layer 300 Lattice transitional function, reduces the polarity effect produced by lattice mismatch.
In conclusion the present invention on active layer 200 by substep, low temperature grow up to be formed a magnesium Delta doping p-type Insert layer 400, since the energy gap for nitrogenizing phosphide material is relatively low, makes magnesium source diffuse into nitride indium layer, increases using moment high magnesium density Add the efficiency of nitride indium layer incorporation magnesium, and then increased the hole concentration of magnesium in p type island region and reduce its activation energy, and then adjust p- The position in n junctions area, lifts the Internal Quantum luminous efficiency of device；The nitride indium layer of low-temperature epitaxy can be reduced to active layer at the same time 200 destruction.
It should be appreciated that above-mentioned specific embodiment is merely a preferred embodiment of the present invention, the present invention is not played Any restrictions act on.Any person of ordinary skill in the field, in the range of technical scheme is not departed from, to this Invent the technical solution disclosed and technology contents make the variation such as any type of equivalent substitution or modification, belong to without departing from this hair The content of bright technical solution, still belongs within protection scope of the present invention.

Claims (10)

  1. A kind of 1. light emitting diode, including at least N-type layer, active layer and the P-type layer stacked gradually, it is characterised in that：In the P Include a p-type insert layer between type layer and the active layer, the p-type insert layer includes periodically stacking successively from bottom to up Indium enriched layer, the first nitride indium layer, magnesium enriched layer and the second nitride indium layer.
  2. A kind of 2. light emitting diode according to claim 1, it is characterised in that：The p-type insert layer and the P-type layer it Between include a transition zone.
  3. A kind of 3. light emitting diode according to claim 2, it is characterised in that：The transition zone is AlxInyGa1-x-yN layers, Wherein, 0≤x ＜ 1,0≤y ＜ 1,0≤x+y ＜ 1.
  4. A kind of 4. preparation method of light emitting diode, including at least following steps：
    Prepare N-type layer；
    In preparing active layer in the N-type layer；
    In preparing P-type layer on the active layer；
    It is characterized in that：The step of P-type layer includes preparing p-type insert layer before preparing, it is specially：
    1) reduces reaction chamber temperature, closes nitrogen source, is passed through indium source, and indium enriched layer is formed in active layer surface；
    2) is passed through nitrogen source, forms the first nitride indium layer；
    3) closes indium source, is passed through magnesium source, forms magnesium enriched layer；
    4) closes magnesium source, continues to be passed through indium source, forms the second nitride indium layer；
    5) repeats the above steps 1) -4), form p-type insert layer.
  5. A kind of 5. preparation method of light emitting diode according to claim 4, it is characterised in that：The life of the indium enriched layer The temperature difference of long temperature and the growth temperature of first nitride indium layer is 0 ~ 50 DEG C.
  6. A kind of 6. preparation method of light emitting diode according to claim 4, it is characterised in that：Second nitride indium layer Growth temperature be greater than or equal to first nitride indium layer, its temperature difference is 0 ~ 50 DEG C.
  7. A kind of 7. preparation method of light emitting diode according to claim 4, it is characterised in that：The p-type insert layer Growth temperature is 400 ~ 800 DEG C.
  8. A kind of 8. preparation method of light emitting diode according to claim 4, it is characterised in that：The p-type insert layer it Include the growth step for preparing a transition zone afterwards.
  9. A kind of 9. preparation method of light emitting diode according to claim 8, it is characterised in that：The transition zone is AlxInyGa1-x-yN layers, wherein, 0≤x ＜ 1,0≤y ＜ 1,0≤x+y ＜ 1.
  10. A kind of 10. preparation method of light emitting diode according to claim 4, it is characterised in that：The step 1) -4) Number of repetition is 1 ~ 10 time.
CN201610320407.1A 2016-05-16 2016-05-16 A kind of light emitting diode and preparation method thereof Active CN105762248B (en)

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US5831277A (en) * 1997-03-19 1998-11-03 Northwestern University III-nitride superlattice structures
US7501299B2 (en) * 2005-11-14 2009-03-10 Palo Alto Research Center Incorporated Method for controlling the structure and surface qualities of a thin film and product produced thereby
EP2985792B1 (en) * 2013-04-12 2019-09-18 Seoul Viosys Co., Ltd. Ultraviolet light-emitting device
CN103824917B (en) * 2014-02-25 2017-01-18 圆融光电科技有限公司 LED manufacturing method, LED and chip
CN103872204B (en) * 2014-03-12 2017-01-04 合肥彩虹蓝光科技有限公司 A kind of p-type interposed layer with loop structure and growing method
CN104009136B (en) * 2014-06-16 2017-01-04 湘能华磊光电股份有限公司 Improve LED outer layer growth method and the LED epitaxial layer of luminous efficiency

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