• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a GaN-based light-emitting diode (1) having an active region (4) disposed between an n-doped layer (2) and a p-doped layer (3) which together form a pn junction, characterized in that the active zone (4) comprises at least one n-doped emissive layer (7-1, 7-2, 7-3, 7-4, 7-5). The invention also relates to a method of manufacturing such a diode.
    公开号:FR3028671A1
    申请号:FR1461201
    申请日:2014-11-19
    公开日:2016-05-20
    发明作者:Ivan-Christophe Robin
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    [0001] TECHNICAL FIELD The field of the invention is that of light-emitting diodes (called LEDs or LEDs), as well as that of light-emitting devices based on such LEDs (screens, projectors, LEDs). walls of images, etc.). STATE OF THE PRIOR ART The technique currently used to manufacture semiconductor-based LEDs consists of producing a pn junction, that is to say bringing into contact electrically a p-doped semiconductor with an n-doped semiconductor. , with, between these doped semiconductors p and n, an intrinsic region, that is to say unintentionally doped. A depletion zone is then obtained at the junction p-n. By passing an electric current through this structure, radiative recombinations of charges (electrons and holes) are then obtained at the level of the depletion zone, causing a light emission. Materials based on GaN (GaN, InGaN, AIGaN) are the materials currently used commercially to produce LEDs in the UV, blue, green or even red for LEDs in the form of nanowires. Indeed, the GaN bandgap energy of 3.42 eV at room temperature makes it possible to obtain UV emission.
    [0002] By adding indium to GaN to form the InGaN alloy, the energy of the forbidden band is lowered which allows to offset the emission wavelengths in the visible. In order to increase the radiative emission efficiency of an LED, quantum wells (QW for Quantum Well) are commonly made in the intrinsic region. This makes it possible to confine the charges in the quantum wells and to prevent these charges from being lost on non-radiative defects. In the most commonly used techniques, the emission is obtained from quantum wells of InGaN alloy with 5 to 30% indium emitting in the blue and into the red. However, the difference in mobility between the electrons and the holes tends to impose a recombination closer to the p-doped semiconductor region, or even in this p-doped region, resulting in a limited radiative emission efficiency. To circumvent this difficulty, one method consists in confining the electrons in the intrinsic region by means of an electron blocking layer (EBL) interposed between the intrinsic region and the p-doped semiconductor region. In this way, it is avoided that the recombinations take place outside the intrinsic region and the rate of radiative recombinations is thus increased. This electron blocking layer is generally made of AIGaN with 8 to 20% aluminum. The realization of this electron blocking layer however complicates the manufacture of the diode. This embodiment indeed requires optimization and calibration of the aluminum flux in addition to those of the gallium and indium streams. In addition, the growth temperature of this EBL layer is different from the growth temperature of the other layers of the diode. In addition, when the diode takes the form of a nanowire, it is not easy to find growth conditions that allow this EBL layer comes to cover homogeneously the flanks of the nanowire. Finally, this EBL layer must be p-doped, which requires doping optimization of AlGaN. Another solution is to standardize the distribution of holes in the quantum wells so as not to see their injection be limited to the only quantum wells closest to the p-doped region. It is therefore proposed to p-type doping, typically using magnesium, barrier layers arranged in the intrinsic region such that each well is disposed between two barrier layers. This solution appears difficult to implement because it is absolutely necessary to avoid the diffusion of the p-type dopant in the quantum wells. The risk is effectively to annihilate the efficiency of radiative recombination in quantum wells, and thus to greatly reduce luminescence.
    [0003] SUMMARY OF THE INVENTION The aim of the invention is to propose a light-emitting diode having an improved radiative recombination rate and a better emission efficiency, while avoiding the aforementioned problems.
    [0004] To this end, it proposes a GaN-based light-emitting diode comprising an active zone disposed between an n-doped layer and a p-doped layer, which together form a pn junction, characterized in that the active zone comprises at least one n-doped emissive layer. . Some preferred but non-limiting aspects of this light-emitting diode are as follows: the active zone comprises a plurality of emissive layers each sandwiched between two barrier layers, and at least the emissive layer closest to the p-doped layer is a layer n-doped emissive; the at least one n-doped emissive layer is sandwiched between two barrier layers of which at least the barrier layer arranged on the p-doped layer side is p-doped; the at least one n-doped emissive layer is sandwiched between two unintentionally doped barrier layers; the doping level n of the at least one emitting layer is at least twice, and at most equal to 100 times, the unintentional doping level of the barrier layers; the n-doped layer and the p-doped layer are GaN layers, the at least one emitting layer is an InGaN layer and the barrier layers are GaN layers.
    [0005] The invention also extends to a method for producing such a light emitting diode comprising doping n of at least one emitting layer of the active zone.
    [0006] BRIEF DESCRIPTION OF THE DRAWINGS Other aspects, objects, advantages and features of the invention will appear better on reading the following detailed description of preferred embodiments thereof, given by way of non-limiting example, and with reference to the accompanying drawings in which: Figure 1 is a diagram showing an embodiment of an LED according to the invention; FIG. 2 represents the internal quantum efficiencies for the electrical injection for different doping levels of the n-doped emissive layer; FIG. 3 represents the distribution of electrons and holes in a diode without intentional doping of the emissive layers and in a diode with n-doping of the emissive layers according to the invention; FIGS. 4A and 4B schematically represent exemplary embodiments of a LED in the form of a nanowire.
    [0007] DETAILED DESCRIPTION OF PARTICULAR EMBODIMENTS Referring firstly to FIG. 1 which schematically represents a light emitting diode 1, or LED 100, according to a particular embodiment. The LED 1 comprises a p-n junction formed by an n-doped layer 2, for example by adding silicon or germanium, and a p-doped layer 3, for example by adding magnesium or carbon. A first metal electrode 5 is disposed against the n-doped layer 2 of the pn junction and forms a cathode of the LED 1, and a second metal electrode 6 is disposed against the p-doped layer 3 of the pn junction and forms an anode of the LED 1.
    [0008] In general, the n 2 doped layer of the pn junction can have a donor concentration of between about 1017 and 1020 donors / cm3, and the p-doped p3 layer of the pn junction can have an acceptor concentration of about 1015 and 1020 acceptors / cm3.
    [0009] The thickness (along the Z axis in FIG. 1) of the n-doped layer 2 of the pn junction is, for example, between 50 nm and 2 μm, and the thickness of the p-doped layer 3 of the junction. pn is for example between 5 nm and 2 um. The n-doped layer 2 is for example an InxnGau_xn) N layer and the p-doped layer 3 is for example a InxpGan_xoN layer, with Xn and Xp the indium compositions typically ranging between 0 and 0.25. In the remainder of the description, the following example will be used: Xn = Xp = 0, the doped layers 2 and 3 then being respectively GaN-n and GaN-p. The LED 1 comprises, between the doped layers 2 and 3, an active zone 4 10 in which radiative recombinations occur producing a light emission of the LED 1. The active zone 4 comprises in particular at least one emitting layer forming a quantum well taken sandwiched between two barrier layers. Thus, in the active zone, there are 4 m emitting layers 7-1, 7-2, 7-3, 7-4, 7-5, m being an integer greater than or equal to 1 and typically less than 50, and 15 m +1 barrier layers 8-1, 8-2, 8-3, 8-4, 8-5, 8-6 such that each emitting layer is disposed between two barrier layers, and therefore the active zone 4 is formed of an alternating stack of emissive layers and barrier layers with in particular a barrier layer 8-1 on the side of the n-doped layer 2 and a barrier layer 8-6 on the p-doped layer side.
    [0010] In the example of FIG. 1, the active zone 4 of the LED 1 comprises five emitting layers 7-1, 7-2, 7-3, 7-4, 7-5 each forming a quantum well. The thickness of each of the emitting layers is between 0.5 and 10 nm, it is 3 nm in the example studied. Each emitting layer is for example a layer of InGaN, with an indium composition which can be between 5 to 30%.
    [0011] And the active area 4 of LED 1 has 6 barrier layers 8-1, 8-2, 8-3, 8-4, 8-5, 8-6 alternating with the emissive layers. The thickness of each of the barrier layers is between 1 nm and 30 nm. The thickness of the barrier layer 8-6 on the p-doped layer side may be greater than that of the other barrier layers 8-1, 8-2, 8-3, 8-4, 8-5 in order to avoid that the dopants, usually magnesium, contained in the p-doped layer do not diffuse into the quantum wells. It is in the studied 30 nm example, while that of the other barrier layers is 10 nm. Each barrier layer is for example a GaN layer. In a preferred embodiment, the LED 1 is devoid of an electron blocking layer between the active zone 4 and the p-doped layer 3 of the p-n junction. The p-doped layer 3 of the pn junction is then in direct contact with the active zone 4. In a possible embodiment, the LED 1 may comprise an electron-blocking layer (not shown) disposed between the active zone 4. and the p-doped layer 3 of the pn junction, for example an AlGaN layer.
    [0012] In the context of the invention, at least one of the emitting layers 7-1, 7-2, 7-3, 7-4, 7-5 is n-doped. This at least one n-doped emissive layer is preferably the emitting layer 7-5 closest to the p-doped layer 3. In a variant, it can be provided that several successive emissive layers on the p-doped layer 3 side are n-doped. for example the three emitting layers 7-3, 7-4 and 7-5. Or that all the emissive layers 7-1, ..., 7-5 are n-doped, as is the case in the example studied. In contrast to the solution of doping the wells for which the injection efficiency of the holes in the quantum wells near the n 2 doped layer is sought, the invention takes note of this low injection efficiency of the holes in the quantum wells farthest from the p-doped layer 3, and instead proposes to increase the electron density in the quantum wells where the holes are actually present, that is to say in the nearest emitting layer or layers of the p-doped layer 3. Since the holes are essentially confined in these emissive layers, and that it is possible, thanks to the doping n of the at least one emissive layer, to increase the electron density, the number of radiative recombinations increases. .
    [0013] In a first variant embodiment, the at least one n-doped emissive layer is sandwiched between two barrier layers whose at least one barrier layer arranged on the p-doped layer side of the p-n junction is p-doped. Taking the example of doping n of the emitting layer 7-5 closest to the p-doped layer 3, the barrier layer 8-6 of the p-doped layer side 3 is then p-doped. Of course, it can also be provided that all or some of the barrier layers are p-doped by addition of magnesium or carbon. Thus, in this variant embodiment, it is also intended to improve the injection efficiency of the holes in the different quantum wells, in particular so that they do not remain locked in the quantum well or wells closest to the p-doped layer. of the pn junction.
    [0014] In one embodiment, the at least one p-doped barrier layer is only partially p-doped to prevent diffusion of the dopant into the adjacent emissive layer (s). Partially doped means that only a selected region of the barrier layer is p-doped, typically a central region that is not in contact with an emissive layer. A partially p-doped barrier layer can thus be decomposed along the Z axis into an unintentionally doped lower sublayer, a p-doped core sublayer, and an unintentionally doped upper sublayer. In a second variant embodiment, the at least one n-doped emissive layer is sandwiched between two unintentionally doped barrier layers. The doping level n of the at least one emitting layer is then at least equal to twice, and at most equal to 100 times, the level of unintentional doping of the barrier layers. Preferably, the n doping level of the at least one emitting layer is at least ten times, and at most fifty times, the unintentional doping level of the barrier layers. The unintentional doping level of the barrier layers is such that the concentration of residual donors is typically between 1016 donors / cm3 and 1018 donors / cm3, preferably less than 5.1017 donors / cm3, for example 1017 donors / cm3. And the doping level n of the at least one emissive layer is thus at most equal to 1020 donors / cm3. FIG. 2 represents the internal quantum efficiencies for the emission of photons for different doping levels of the n-doped emissive layer of the studied LED which is recalled that it comprises five InGaN emitting layers of 3 nm thick sandwiched between GaN barrier layers 10 nm thick, except for the nearest 8-6 of the p-junction p 3 layer of the pn junction which is 30 nm thick. The n-doped layer 2 of the p-n junction has a doping of 1019 donors / cm 2 and the p-n doped layer 3 of the p-n junction has a doping of 1019 acceptors / cm 3. The unintentional doping of the barrier layers is 1017 5 donors / cm3 and the n-doping ("n_QW") of the emissive layers is either 1017 donors / cm3 (top in Figure 2), or 5.1018 donors / cm3 (in bottom in Figure 2). It can be seen that the internal quantum efficiency IQE, expressed as a function of the current density Dc (in A / cm2), increases when the dopant concentration n of the wells increases, and this at low current densities. The maximum efficiency thus goes from about 70% to over 90%. FIG. 3 shows the distribution of the electrons (represented by crosses) and holes (represented by diamonds) in a diode according to the invention with n-doping ("n_QW") of the emissive layers which is either 1017 donors / cm. 3 (top in FIG. 3), that is 5.1018 donors / cm3 (bottom in FIG. 3). It is found that the electron density is increased in the well 7-5 closest to the p-doped layer 3 of the p-n junction when this well is n-doped. The charges are then better balanced in this well 7-5 and the number of radiative recombinations is thus increased. Such an LED 1 operates regardless of the orientation of the structure, whether in the plane c (in the presence of a strong internal electric field), the plane M, 20 in semi-polar, etc. The LED 1 can be made in the form of a planar diode as shown in FIG. 1, that is to say in the form of a stack of layers formed on a substrate (the substrate not being represented on Figure 1), the main faces of the different layers being arranged parallel to the plane of the substrate (parallel to the plane (X, Y)). An embodiment of the LED 1 in the form of such a planar diode is as follows. Firstly, the growth of a first GaN layer having a thickness of between 1 and 4 μm on a sapphire substrate, for example by MOCVD ("MetalOrganic Chemical Vapor Deposition" in English), at a temperature of 3028671 between 950 and 1100 ° C. This growth is completed by forming the layer 2 of GaN-n doped with silicon, with a thickness of between 50 nm and 2 μm. The active zone 4 is then made by not doping the barriers but by doping the quantum wells (emitting layers).
    [0015] The temperature is first lowered in the range 790-860 ° C to grow at a growth rate of about 250 nm / h a 10 nm thick, unintentionally doped barrier layer, forming layer 8. 1. The temperature is then lowered between 700 and 800 ° C to grow a first doped emitting layer 71 at a growth rate of between 30 and 100 nm / h. Silicon doping is achieved during the growth of the emissive layer using a silane stream. These barrier layer and emissive layer growth steps are then repeated until the active zone is finalized. It takes about 100s to grow an emissive layer, which leaves enough time to selectively dope the emissive layers and not the barriers.
    [0016] The temperature is then raised between 980 ° C and 1100 ° C to grow the magnesium-doped GaN-p layer 3 and of thickness between 5 nm and 111 m. The second metal electrode 6 is then made in the form of a Ni / Au layer on the p-doped layer 3, and the first metal electrode 5 is finally made in the form of a Ti / Au layer on the layer. doped n 2 (after separation of the doped layer n 2 with the first layer of GaN with a thickness of between 1 and 4 μm). Alternatively, LED 1 may be in the form of nanowires. FIG. 4A shows such an LED 1 produced in the form of axial nanowires, these nanowires 25 comprising a stack formed of the first electrode 5, a semiconductor substrate 9 (for example gallium) of the n-type, a nucleation layer 10 for the growth of the nanowires, the n-doped layer 2, the active area 4, the p-doped layer 3, and the second electrode 6. An insulating material 11 may surround at least a portion of these nanowires that extend parallel to the Z axis.
    [0017] FIG. 4B represents an LED 1 made in the form of radial nanowires, these nanowires comprising a stack formed of the first electrode 5, the semiconductor substrate 9, the nucleation layer 10 and the n 2 doped layer. Insulating portions 11 partially surround the n-doped layer 2 and the nucleation layer 10. The active zone 4 is made such that it surrounds at least a portion of the n-doped layer 2. The p-doped layer 3 is produced as it surrounds the active zone 4. Finally, the second electrode 6 is made by covering the p-doped layer 3. In a variant of the two embodiments described in FIGS. 4A and 4B, the structure of these nanowires can be reversed, with in this case a semiconductor substrate 9, for example p-type gallium nitride on which the p-doped layer 3 is made, then the other elements of the LED 1 in the reverse order of that described on FIG. Figures 4A and 4 B. The invention is not limited to the LED as previously described but also relates to a method of producing such an LED, wherein the formation of the active zone comprises the production of at least one n-doped emissive layer. According to this method, the at least one emitting layer can be produced by growth at a growth rate of between 30 and 100 nm / h. On the other hand, the layers of the light emitting diode may be planar layers grown one above the other, or layers grown in the form of radial or axial nanowires.
    权利要求:
    Claims (14)
    [0001]
    REVENDICATIONS1. GaN-based light-emitting diode (1) having an active region (4) disposed between an n-doped layer (2) and a p-doped layer (3) which together form a pn junction, characterized in that the active region (4) ) comprises at least one n-doped emitting layer (7-1, 7-2, 7-3, 7-4, 7-5).
    [0002]
    The electroluminescent diode (1) according to claim 1, wherein the active region (4) comprises a plurality of emitting layers (7-1, 7-2, 7-3, 7-4, 7-5) each sandwich between two barrier layers (8-1, 8-2, 8-3, 8-4, 8-5, 8-6), and wherein at least the emissive layer (7-5) closest to the layer doped p (3) is an n-doped emissive layer.
    [0003]
    3. Electroluminescent diode (1) according to one of claims 1 and 2, wherein the at least one n-doped emissive layer (7-5) is sandwiched between two barrier layers (8-5, 8-6) at least the barrier layer (8-6) arranged on the side of the p-doped layer is p-doped.
    [0004]
    The light-emitting diode (1) according to one of claims 1 and 2, wherein the at least one n-doped emitting layer (7-1, 7-2, 7-3, 7-4, 7-5) is sandwiched between two unintentionally doped barrier layers (8-1, 8-2, 8-3, 8-4, 8-5, 8-6).
    [0005]
    The light-emitting diode (1) according to claim 4, wherein the n-doping level of the at least one emitting layer (7-1, 7-2, 7-3, 7-4, 7-5) is at less than twice and not more than 100 times the level of unintentional doping of the barrier layers (8-1, 8-2, 8-3, 8-4, 8-5, 8-6).
    [0006]
    The light-emitting diode (1) according to claim 5, wherein the n-doping level of the at least one emitting layer (7-1,
    [0007]
    7-2, 7-3, 7-4, 7-5) is at least ten times, and at most fifty times, the unintentional doping level of the barrier layers (8-1,
    [0008]
    8-2, 8-3, 8-4, 8-5, 8-6). Electroluminescent diode (1) according to one of claims 4 to 6, wherein the unintentional doping level of the barrier layers (8-1, 8-2, 8-3, 8-4, 8-5, 8-6) is between 1016 donors / cm3 and 1020 donors / cm3. 8. Electroluminescent diode (1) according to one of claims 1 to 7, wherein the doping level n of the at least one emitting layer (7-1, 7-2, 7-3, 7-4, 7 -5) 10 is at most equal to 1020 donors / cm3.
    [0009]
    Electroluminescent diode according to one of Claims 1 to 8, in which the n-doped layer (2) and the p-doped layer (3) are GaN layers, the at least one emitting layer (7-1, 7). -2, 7-3, 7-4, 7-5) is a layer of InGaN and the barrier layers 15 (8-1, 8-2, 8-3, 8-4, 8-5, 8-6 ) are GaN layers.
    [0010]
    10. Electroluminescent diode (1) according to one of claims 1 to 9, devoid of an electron blocking layer between the active zone (4) and the doped layer 13 (3). 20
    [0011]
    11. light-emitting diode (1) according to one of claims 1 to 10, wherein the nearest barrier layer (8-6) of the p-doped layer (3) has a greater thickness than the other barrier layer or layers (8-1, 8-2, 8-3, 8-4, 8-5). 25
    [0012]
    A method of producing a light-emitting diode (1) having an active region (4) disposed between an n-doped layer (2) and a p-doped layer (3) which together form a pn junction, wherein the formation of the active region (4) comprising producing at least one n-doped emitting layer (7-1, 7-2, 7-3, 7-4, 7-5). 30
    [0013]
    The process according to claim 10, wherein the at least one emitting layer (7-1, 7-2, 7-3, 7-4, 7-5) is grown at a growth rate of between and 100 nm / h. 3028671 13
    [0014]
    The method according to one of claims 12 and 13, wherein the layers of the light emitting diode are planar layers grown one above the other, or wherein the layers of the light emitting diode are grown by growth. in the form of radial or axial nanowires.
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1461201A|FR3028671B1|2014-11-19|2014-11-19|DOPED QUANTUM WELL ELECTROLUMINESCENT DIODE AND METHOD FOR MANUFACTURING THE SAME|
    FR1461201|2014-11-19|FR1461201A| FR3028671B1|2014-11-19|2014-11-19|DOPED QUANTUM WELL ELECTROLUMINESCENT DIODE AND METHOD FOR MANUFACTURING THE SAME|
    US14/938,058| US9515220B2|2014-11-19|2015-11-11|Light emitting diode with doped quantum wells and associated manufacturing method|
    EP15194366.9A| EP3024037B1|2014-11-19|2015-11-12|Light emitting diode with doped quantum wells and corresponding method of fabrication|
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