CN100479210C - Multiple quantum well nitride light emitting diode with carrier supplying layer - Google Patents

Multiple quantum well nitride light emitting diode with carrier supplying layer Download PDF

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CN100479210C
CN100479210C CNB2006101427353A CN200610142735A CN100479210C CN 100479210 C CN100479210 C CN 100479210C CN B2006101427353 A CNB2006101427353 A CN B2006101427353A CN 200610142735 A CN200610142735 A CN 200610142735A CN 100479210 C CN100479210 C CN 100479210C
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quantum trap
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barrier layer
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武良文
简奉任
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Epistar Corp
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Formosa Epitaxy Inc
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Abstract

The present invention provides a structure of a multiplex quantum-well luminous electrode, wherein, a carrier providing layer is arranged at one side of a luminous layer to provide the extra carrier for the luminous layer to take part in the new combination, thereby preventing/reducing the foreign matters in the luminous layer. The carrier providing layer comprises multiplex well layer and position-barrier layer, which are alternatively piled in the thickness of 5 to 300, so that the total thickness of the carrier providing layer is 1 to 500 nm. The well layer and the position-barrier layer are made of the compound semi-conductor AlpInqGa1-pN (p and q are equal to or more than zero, p plus q is equal to or more than zero and is equal to or less than one) mixed with Si or Ge, but each of the well layer and the position-barrier layer has different compositions, wherein, the position-barrier layer is higher than the energy-band gas of the well layer. The electron thickness of the carrier providing layer is between 1*10<17> and 5*10<21> cm<3>.

Description

Have carrier provide the layer the multiple quantum trap iii-nitride light emitting devices
The invention technical field
The invention relates to the nitride multiple quantum trap luminous diode, particularly have a nitride multiple quantum trap luminous diode that carrier provides layer about a kind of, so as to extra carrier is provided, and the use of avoiding/reduces the interior impurity of luminescent layer.
Background technology
In order to improve the brightness of gallium nitride (GaN) series LED (LED), U.S. Patent No. 5,578,839 have disclosed the In that a kind of luminescent layer (or claiming active layers) is doped with n type impurity (for example Si) and/or p type impurity (for example Mg or Zn etc.) xGa 1-xThe made LED structure of N (0＜x＜1) compound semiconductor.The luminescent layer of this LED structure is to be clipped in the middle of second coating layer that first coating layer (clad layer) that n type GaN based compound semiconductor makes and p type GaN based compound semiconductor make.This LED structure lifting in brightness, be since in the above-mentioned luminescent layer impurity that mixed improved the density of carrier (that is, electronics and electric hole), therefore have more overloading participate in again in conjunction with due to (recombination).
By contrast, (multi quantum-well, the MQW) high-brightness LED of technology are to adopt the well layer (well layer) that does not add doping in its luminescent layer usually to use multiple quantum trap.The luminescent layer of general MQW LED is to include multiple well layer, and the thickness of well layer is less than the De Buluoyi of carrier in the semi-conducting material (deBroglie) wavelength, causes electronics and electric hole to be limited in the well layer, and can reach better joint efficiency again.The well layer does not normally add doping, because the impurity in the well layer can cause the combination again of non-radiation type (non-radiative), and then causes the reduction of luminous efficiency and the too much generation of heat.On the other hand, in in May, 2002 Electrical Engineer association quantum electronics periodical (IEEE Journal of Quantum Electronics) the 38th the 5th phase, people such as Wu advise in Influence of Si doping on the Characteristics of InGaN-GaN MultipleQuantum-Well Blue Light Emitting Diode (Si mixes up the influence aspect the characteristic of an InGaN-GaN multiple quantum trap luminous diode) literary composition, luminous intensity and the operating voltage of InGaN-GaN MQW LED, can mix up by in the GaN of MQW luminescent layer potential barrier layer (barrierlayer), adding Si, and be significantly improved.Yet it is down accurate that the impurity density in the potential barrier layer should maintain suitable position, otherwise the crystallization of this LED (crystalline) just can be affected.
In other words, mix up impurity, help to improve carrier joint efficiency again really, but this kind improvement is to pay a price at the luminescent layer of LED.
Summary of the invention
Therefore, main purpose of the present invention provides a kind of nitride MQW LED structure, so as to exempting the shortcoming of prior art.
A principal character of the present invention is in the LED structure that is proposed, and provides carrier that layer (a carrier supply layer) is provided in a side of unadulterated MQW luminescent layer.It is to include well layer and potential barrier layer multiple and that alternately overlap each other that this carrier provides layer, and these well layers and potential barrier layer respectively have Thickness, be 1～500nm and make carrier that layer gross thickness is provided.Well layer and potential barrier layer all are by the Al that is doped with Si or Ge pIn qGa 1-p-qN (p, q 〉=0,0≤p+q≤1) compound semiconductor is made, but has different compositions, and potential barrier layer need have the band gap (bandgap) that is higher than the well layer.In addition, carrier provide the layer electron concentration be 1 * 10 17～5 * 10 21/ cm 3
Carrier provides the setting of layer to have multiple advantages.At first, extra electronics can be provided in the MQW luminescent layer combining again with electric hole, and makes LED structure of the present invention reach higher internal quantum (internal quantum efficiency) and higher brightness.In addition, because movement of electrons (mobility) is greater than electric hole, carrier provides the setting of layer that electronics is slowed down, so that electronics has higher chance to combine again with electric hole, thereby can reach higher joint efficiency again.Moreover the operating voltage that mixing up carrier into provides Si in the layer or Ge can make LED structure of the present invention effectively under the situation of luminescent layer that undopes reduces, and can make luminescent layer that more crystalline is arranged.
Another feature of the present invention is what carrier provided layer and luminescent layer centre electric hole barrier layer (hole blocking layer) to be set.This electric hole barrier layer is to be made by the GaN based material that does not mix or have Si to mix, and it has greater than the band gap of luminescent layer provides in the layer and at this place and combine again with electronics to avoid the electric hole carrier of escaping into.Electricity hole barrier layer has Thickness.
The setting of electricity hole barrier layer also has some extra advantages.For example, experimental results show that the existence of electric hole barrier layer can make breakdown voltage (breakdown voltage) increase, and the leakage current (leakage current) of LED structure of the present invention is reduced.In addition, because carrier provides the flaw that has some V-arrangements on the surface after layer is grown up to form, electric hole barrier layer can remedy the luminescent layer that these flaws make follow-up growth and reach preferable crystallization.In certain embodiments of the present invention, electric hole barrier layer is made by the GaN based material that In mixes or In/Si mixes jointly, to reach better smoothing effect.Its reason is can significantly promote the surface smoothing that carrier provides layer when adding phosphide atom, and then avoids the flaw and the storehouse fault (stacking faults) of luminescent layer effectively.
Now in conjunction with detailed description and the claim protection range of institute's accompanying drawing, embodiment, after above-mentioned and of the present invention other purpose and advantage be specified in.Yet, be to establish when understanding institute's accompanying drawing pure for explaining orally spirit of the present invention, should not be considered as the definition of category of the present invention.The definition of relevant category of the present invention please refer to claims.
Description of drawings
Shown in Figure 1 is schematic diagram according to the nitride MQW LED structure of the first embodiment of the present invention.
Shown in Figure 2 is schematic diagram according to the nitride MQW LED structure of the second embodiment of the present invention.
Shown in Figure 3 is the schematic diagram of the LED matrix of LED structure behind the process chip program of Fig. 1.
The primary clustering symbol description
10 substrates, 20 resilient coatings
30 first contact layers, 40 carriers provide layer
41 well layers, 42 potential barrier layer
50 luminescent layers, 51 well layers
52 potential barrier layers, 60 second contact layers
70 electric hole barrier layer 80 transparency conducting layers
91 first electrodes, 92 second electrodes
Embodiment
Shown in Figure 1 is schematic diagram according to the nitride MQW LED structure of the first embodiment of the present invention.Note that this specification is to use " LED structure " speech to censure the epitaxial structure of a LED, censure after LED structure forms with " LED matrix " speech in addition, pass through the semiconductor device of follow-up chip program (chip process) gained after forming electrode on the LED structure again.
As shown in Figure 1, in the bottom of above-mentioned LED structure, substrate 10 is normally with alumina single crystal (sapphire) or have with the oxide monocrystal of the approaching lattice constant of the epitaxial layer of LED structure and make.This substrate 10 also can be by SiC (6H-SiC or 4H-SiC), Si, ZnO, GaAs or MgAl 2O 4Make.Usually, aforesaid substrate 10 modal materials are sapphire or SiC.At the upper surface of this substrate 10, then form by Al aGa bIn 1-a-bThe resilient coating (buffer layer) 20 that N (0≤a, b＜1, a+b≤1) makes.Note that in certain embodiments, resilient coating 20 also can omit.What also please note is, because it is applied in the epitaxial layer that forms LED structure of the present invention, mostly be the known semiconductor making method of personnel that association area possesses general skill, for simplicity, how the details of these methods is omitted in this specification, unless important the creating conditions that some is specific, just understood and pointed out.
At the upper surface of above-mentioned resilient coating 20, form first contact layer made from the first conductivity type GaN based material (contact layer) 30.In the present embodiment, first contact layer 30 is to make with a kind of n type GaN based material.In some alloytype embodiment, first contact layer 30 also can be made by a kind of p type GaN based material.The purpose of first contact layer 30 is set, and is in follow-up chip program, provides formed n type electrode required nurse difficult to understand contact (ohmic contact), and provides preferable growth condition for the epitaxial layer of other follow-up growth.
Then, at the upper surface of above-mentioned first contact layer 30, form carrier layer 40 is provided.It is to replace storehouse by two-layer at least well layer 41 and two-layer at least potential barrier layer 42 to form that carrier provides layer 40.It is between 1nm and 500nm that carrier provides layer 40 gross thickness, and the thickness of each well layer 41 and potential barrier layer 42 be
Figure C20061014273500091
With
Figure C20061014273500092
Between.These well layers 41 and potential barrier layer 42 all are by the Al that is doped with Si or Ge pIn qGa 1-p-qN (p, q 〉=0,0≤p+q≤1) compound semiconductor is made, and has 1 * 10 17/ cm 3With 5 * 10 21/ cm 3Between electron concentration.These well layers 41 and potential barrier layer 42 are to have independently to form, and are high band gap (Eg) but potential barrier layer 42 has than well layer 41.Well layer 41 and potential barrier layer 42 all are to form under the growth temperature between 600 ℃ and 1200 ℃, but potential barrier layer 42 has higher growth temperature.
Then, provide layer 40 upper surface, form the MQW luminescent layer 50 of present embodiment at carrier.MQW luminescent layer 50 is to replace storehouse by the well layer 51 of majority and most potential barrier layers 52 to form.Well layer 51 and potential barrier layer 52 all are by the Al that does not add doping xIn yGa 1-x-yN (x, y 〉=0,0≤x+y≤1) compound semiconductor is made, and forms but respectively have independently, and it is high band gap (Eg) that this potential barrier layer 52 has than the well layer.These well layers 51 and potential barrier layer 52 also be 600 ℃ with 1200 ℃ between different growth temperature under form, but potential barrier layer 52 has higher growth temperature.Carrier provides the well layer 41 of layer 40, is to have suitable Al pIn qGa 1-p-qN (p, q 〉=0,0≤p+q≤1) forms, and makes the Al of its band gap greater than the well layer 51 of luminescent layer 50 xIn yGa 1-x-yN (x, y 〉=0,0≤x+y≤1).Note that luminescent layer 50 structures of present embodiment only belong to illustration, spirit of the present invention does not limit luminescent layer 50 needs a specific MQW structure.
Acting on and providing extra electron to enter in the MQW luminescent layer 50 of layer 40 is provided carrier, so that combine again with electric hole, and makes LED structure of the present invention reach higher internal quantum and and then reaches higher brightness.In addition, be greater than electric hole owing to movement of electrons is known, carrier provides the setting of layer 40 that electronics is slowed down, and makes it have higher chance to combine again with electric hole, thereby can reach higher joint efficiency again.Further be, mixing up into, carrier provides Si or Ge in the layer 40 can make LED structure of the present invention, can reduce operating voltage effectively equally under the situation of luminescent layer 50 that undopes, in addition, carrier provides layer 40 can impel the luminescent layer 50 of follow-up growth to have more crystalline again.
At last, at the upper surface of luminescent layer 50, form second contact layer 60 with the second conductivity type GaN based material opposite with first conductivity type.Therefore, in the present embodiment, second contact layer 60 is to make (with the n type GaN based material with respect to first contact layer 30) with a kind of p type GaN based material.In some other embodiment, second contact layer 60 also can be made by n type GaN based material.The purpose that second contact layer 60 is set is in follow-up chip program, and the required nurse contact difficult to understand of p type electrode of follow-up formation is provided.
Shown in Figure 2 is schematic diagram according to the nitride MQW LED structure of the second embodiment of the present invention.Basically, present embodiment structurally is similar with first embodiment, and unique not existing together is to be that carrier provides between layer 40 and the luminescent layer 50 to be provided with the electric hole of one deck barrier layer 70.Provide two most important reasons of electric hole barrier layer 70 to be: (1) avoids the electric hole of luminescent layer 50 to escape to carrier to be provided layer 40 and combines again with non-illumination mode with electronics at this place; And (2) make its surface go up the smoothing of formed V-arrangement flaw, and make the luminescent layer 50 of follow-up growth can reach preferable crystallization after carrier provides layer 40 growth.
Electricity hole barrier layer 70 is under the growth temperature between 600 ℃ and 1200 ℃, not add the GaN based material that mixes or have Si to mix or have In to mix or have In/Si to mix jointly, is formed on the upper surface that carrier provides layer 40, and has
Figure C20061014273500111
Between thickness.The material of electricity hole barrier layer 70 has band gap greater than luminescent layer 50 at cording, provides in the layer 40 to avoid electric hole to escape entering carrier.Purpose with In doping is further to promote the surface smoothing that carrier provides layer 40, with flaw and the storehouse fault of avoiding luminescent layer 50 effectively.Still has other extra advantage according to the existence that experiment showed, electric hole barrier layer 70, such as the breakdown voltage (V that makes LED structure of the present invention b) increase, and make its leakage current (I r) reduce.
Traditionally, LED structure illustrated in figures 1 and 2 then needs through chip program with the electrode that forms the external electric binding of LED and prepare this LED in order to encapsulation.Shown in Figure 3 is the schematic diagram of the LED matrix of LED structure behind this chip program of process of Fig. 1.Noting that to be that identical chip program can be applied to LED structure shown in Figure 2 equally, but for simplicity, hereinafter is that LED structure with Fig. 1 is as example.
At first, the LED structure is by suitably in addition etching, so as to exposing the part upper surface of first contact layer 30.Then, first contact layer 30 be exposed the zone upper surface, form first electrode 91 with the proper metal material.On the other hand, at the upper surface of second contact layer 60, form a transparency conducting layer (transparent conductive layer) 80.This transparency conducting layer 80 can be a metal conducting layer (metallic conductive layer) or transparent oxide layer (transparent oxidelayer).These metallic conduction series of strata are by following material but to be not limited only to these materials made: Ni/Au alloy, Ni/Pt alloy, Ni/Pd alloy, Pd/Au alloy, Pt/Au alloy, Cr/Au alloy, Ni/Au/Be alloy, Ni/Cr/Au alloy, Ni/Pt/Au alloy and Ni/Pd/Au alloy.On the other hand, the transparent oxide series of strata are by following material but to be not limited only to these materials made: ITO, CTO, ZnO:Al, ZnGa 2O 4, SnO 2: Sb, Ga 2O 3-: Sn, AgInO 2: Sn, In 2O 3: Zn, CuAlO 2, LaCuOS, NiO, CuGaO 2, and SrCu 2O 2Next, at the upper surface of transparency conducting layer 80 or side as shown in Figure 3, form second electrode 92 at transparent conductive layer 80.Second electrode 92 is by following material but to be not limited only to these materials made: Ni/Au alloy, Ni/Pt alloy, Ni/Pd alloy, Ni/Co alloy, Pd/Au alloy, Pt/Au alloy, Ti/Au alloy, Cr/Au alloy, Sn/Au alloy, Ta/Au alloy, TiN, TiWN x(x 〉=0) and WSi y(y 〉=0).
By the above detailed description of preferred embodiments, be to wish to know more the feature and spirit of describing this present invention, and be not to come category of the present invention is limited with above-mentioned disclosed preferred embodiment.On the contrary, its objective is that hope can contain in the category of claim of being arranged in of various changes and tool equality institute of the present invention desire application.

Claims (27)

1. nitride multiple quantum trap LED structure comprises at least:
Substrate;
First contact layer is to be positioned at this substrate top, and this first contact layer is to be made by the GaN based material with first conductivity type;
Carrier provides layer, it is the top that is positioned at this first contact layer, it is to replace storehouse by two-layer at least well layer and two-layer at least potential barrier layer to form that this carrier provides layer, and each is made this well layer and this potential barrier layer by the GaN based material that is doped with n type impurity, and this potential barrier layer has the band gap that is higher than this well layer;
Luminescent layer is to be positioned at this carrier layer top, this luminescent layer are provided is to have the multiple quantum trap structure that well layer and potential barrier layer by plural layer are constituted, and this well layer and this potential barrier layer are respectively made by the GaN based material; And
Second contact layer is to be positioned at this luminescent layer top, and this second contact layer is to be made by the GaN based material with second conductivity type opposite with this first conductivity type;
Wherein, this carrier provides this well layer of layer to have the band gap of this well layer that is higher than this luminescent layer.
2. nitride multiple quantum trap LED structure according to claim 1 further comprises resilient coating, is that this resilient coating is to make with the GaN based material between this substrate and this first contact layer.
3. nitride multiple quantum trap LED structure according to claim 2, wherein, this GaN based material of this resilient coating is Al aGa bIn 1-a-bN (0≤a, b＜1, a+b≤1).
4. nitride multiple quantum trap LED structure according to claim 1, wherein, this carrier provide this well layer of layer and this n type impurity of this potential barrier layer be Si and Ge the two one of.
5. according to claim 1 a described nitride multiple quantum trap LED structure, wherein, it is respectively to have that this carrier provides this well layer and the potential barrier layer of layer
Figure C2006101427350002C1
Between thickness.
6. according to claim 1 a described nitride multiple quantum trap LED structure, wherein, it is the thickness that has between 1nm～500nm that this carrier provides layer.
7. according to claim 1 a described nitride multiple quantum trap LED structure, wherein, it is to have 1 * 10 that this carrier provides layer 17/ cm 3～5 * 10 21/ cm 3Between electron concentration.
8. according to claim 1 a described nitride multiple quantum trap LED structure, wherein, this GaN based material of this well layer of this luminescent layer and this potential barrier layer is Al xIn yGa 1-x-yN (x, y 〉=0,0≤x+y≤1).
9. according to claim 1 a described nitride multiple quantum trap LED structure, wherein, this GaN based material of this well layer of this luminescent layer and this potential barrier layer is not add doping.
10. nitride multiple quantum trap LED structure according to claim 1, wherein, this GaN based material of this well layer of this luminescent layer and this potential barrier layer is Al pIn qGa 1-p-qN (p, q 〉=0,0≤p+q≤1).
11. nitride multiple quantum trap LED structure according to claim 1, further comprise this carrier provide the layer and this luminescent layer between electric hole barrier layer, this electricity hole barrier layer is to be made by the GaN based material with the band gap that is higher than this luminescent layer.
12. nitride multiple quantum trap LED structure according to claim 11, wherein, this electricity hole barrier layer is to have
Figure C2006101427350003C1
Between thickness.
13. according to claim 11 a described nitride multiple quantum trap LED structure, wherein, this GaN based material of this electricity hole barrier layer is not add doping.
14. nitride multiple quantum trap LED structure according to claim 11, wherein, this GaN based material of this electricity hole barrier layer is doped with an impurity, this impurity be Si, In, with the Si/In thrin.
15. a nitride multiple quantum trap LED matrix comprises at least:
Substrate;
Resilient coating is to be positioned at this substrate top, and this resilient coating is with Al aGa bIn 1-a-bN (0≤a, b＜1, a+b≤1) makes;
First contact layer is to be positioned at this resilient coating top, and this first contact layer is to be made by the GaN based material with first conductivity type;
Carrier provides layer, it is the part upper surface that is positioned at the top of this first contact layer and covers this first contact layer, it is to replace storehouse by two-layer at least well layer and two-layer at least potential barrier layer to form that this carrier provides layer, and this well layer and this potential barrier layer are respectively by the Al that is doped with n type impurity pIn qGa 1-p-qN (p, q 〉=0,0≤p+q≤1) makes, and this potential barrier layer has the band gap that is higher than this well layer;
First electrode is the upper surface that this first contact layer of position is not provided layer to cover by this carrier;
Luminescent layer is to be positioned at this carrier layer top, this luminescent layer are provided is to have the multiple quantum trap structure that well layer and potential barrier layer by plural layer are constituted, and this well layer and this potential barrier layer are respectively by Al xIn yGa 1-x-yN (x, y 〉=0,0≤x+y≤1) makes; And
Second contact layer is to be positioned at this luminescent layer top, and this second contact layer is to be made by the GaN based material with second conductivity type opposite with this first conductivity type;
Transparency conducting layer is at least one part upper surface that is positioned at this second contact layer, this transparency conducting layer be a metal conducting layer and transparent oxide layer the two one of; And
Second electrode is to be positioned on this transparency conducting layer, or is positioned at the upper surface that this second contact layer is not covered by this transparency conducting layer;
Wherein, this carrier provides this well layer of layer to have the band gap of this well layer that is higher than this luminescent layer.
16. nitride multiple quantum trap LED matrix according to claim 15, wherein, this carrier provide this well layer of layer and this n type impurity of this potential barrier layer be Si and Ge the two one of.
17. nitride multiple quantum trap LED matrix according to claim 15, wherein, this carrier provides this well layer and potential barrier layer of layer, is respectively to have
Figure C2006101427350004C1
Between thickness.
18. nitride multiple quantum trap LED matrix according to claim 15, wherein, it is the thickness that has between 1nm～500nm that this carrier provides layer.
19. nitride multiple quantum trap LED matrix according to claim 15, wherein, it is to have 1 * 10 that this carrier provides layer 17/ cm 3～5 * 10 21/ cm 3Between electron concentration.
20. nitride multiple quantum trap LED matrix according to claim 15, wherein, this GaN based material of this well layer of this luminescent layer and this potential barrier layer is not add doping.
21. according to claim 15 a described nitride multiple quantum trap LED matrix, further comprise this carrier provide the layer and this luminescent layer between electric hole barrier layer, this electricity hole barrier layer is to be made by the GaN based material with the band gap that is higher than this luminescent layer.
22. nitride multiple quantum trap LED matrix according to claim 21, wherein, this electricity hole barrier layer is to have
Figure C2006101427350004C2
Between thickness.
23. nitride multiple quantum trap LED matrix according to claim 21, wherein, this GaN based material of this electricity hole barrier layer is not add doping.
24. according to the described nitride multiple quantum trap LED matrix of claim 21, wherein, this GaN based material of this electricity hole barrier layer is doped with an impurity, this impurity be Si, In, with the Si/In thrin.
25. nitride multiple quantum trap LED matrix according to claim 15, wherein, this metal conducting layer is to be made of a kind of institute that is selected from the following material: Ni/Au alloy, Ni/Pt alloy, Ni/Pd alloy, Pd/Au alloy, Pt/Au alloy, Cr/Au alloy, Ni/Au/Be alloy, Ni/Cr/Au alloy, Ni/Pt/Au alloy and Ni/Pd/Au alloy.
26. nitride multiple quantum trap LED matrix according to claim 15, wherein, this transparent oxide layer is to be made of a kind of institute that is selected from the following material: ITO, CTO, ZnO:Al, ZnGa 2O 4, SnO 2: Sb, Ga 2O 3: Sn, AgInO 2: Sn, In 2O 3: Zn, CuAlO 2, LaCuOS, NiO, CuGaO 2And SrCu 2O 2
27. nitride multiple quantum trap LED matrix according to claim 15, wherein, this second electrode is to be made of a kind of institute that is selected from the following material: Ni/Au alloy, Ni/Pt alloy, Ni/Pd alloy, Ni/Co alloy, Pd/Au alloy, Pt/Au alloy, Ti/Au alloy, Cr/Au alloy, Sn/Au alloy, Ta/Au alloy, TiN, TiWN x(x 〉=0) and WSi y(y 〉=0).
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