CN114864783A - Ultraviolet light-emitting diode structure - Google Patents
Ultraviolet light-emitting diode structure Download PDFInfo
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/36—Semiconductor devices having potential barriers 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 electrodes
- H01L33/40—Materials therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers 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 having potential barriers 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 having potential barriers 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
- H01L33/04—Semiconductor devices having potential barriers 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 quantum effect structure or superlattice, e.g. tunnel junction
- H01L33/06—Semiconductor devices having potential barriers 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 quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers 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 having potential barriers 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 Table
- H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
- H01L33/325—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen characterised by the doping materials
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L2933/0016—Processes relating to electrodes
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Abstract
The invention provides an ultraviolet light-emitting diode structure which comprises a substrate and an epitaxial layer grown on the substrate; the epitaxial layer comprises a buffer layer, an AlGaN layer, a nAlGaN layer, a first metal electrode layer, a multi-quantum well light-emitting layer, a pAlGaN layer, a second metal electrode layer and a PGaN layer which are sequentially stacked from the substrate, wherein the Al component ratio of the pAlGaN layer to the second metal electrode layer is a preset ratio; the area of the multiple quantum well light-emitting layer is the same as that of the pAlGaN layer and is smaller than that of the nAlGaN layer; the area of the PGaN layer is smaller than that of the pAlGaN layer; the first metal electrode layer and the nAlGaN layer form ohmic contact; the second metal electrode layer comprises a first P electrode and a second P electrode, and the first P electrode is connected with the second P electrode or not connected with the second P electrode; the second P electrode and the PGaN layer form ohmic contact; the first P-electrode forms an ohmic contact with a portion of the pAlGaN layer not covered by the PGaN layer. The invention can respectively realize ohmic contact between the pAlGaN layer and the metal electrode layer thereon and between the pGaN layer and the metal electrode layer thereon, thereby further improving the light-emitting efficiency.
Description
Technical Field
The invention relates to the technical field of LED chips, in particular to an ultraviolet light-emitting diode structure.
Background
In general, a low-luminance UVC LED is composed of a substrate, an AlN layer, a nAlGaN layer, an active layer, a pAlGaN layer, a pGaN layer, and the like, and if a UVC LED epitaxial wafer thus composed is fabricated into a UVC LED chip by chip processing. As is clear from the absorption range of GaN, GaN has the property of absorbing all light of 3.4eV (360nm) or less. Since the wavelength range of UVC is within the absorption range of GaN, when pGaN is used as an electrode layer, although it is easy to achieve improvement in luminous efficiency, light toward pGaN layer is absorbed by pGaN layer in UVC wavelengths generated from an active layer, and thus light extraction efficiency is lowered. Further, in the UVC LED structure, ohmic contact is difficult to form due to the presence of pAlGaN, and thus an operating voltage is likely to increase. Therefore, most of the manufactured chip products are low-luminance products with low light emitting efficiency.
Disclosure of Invention
In order to solve the problem of low light emitting efficiency of the UVC LED in the above problems, the invention provides an ultraviolet light emitting diode structure, which comprises a substrate and an epitaxial layer grown on the substrate;
the epitaxial layer comprises an AlN buffer layer, an AlGaN layer, a nAlGaN layer, a first metal electrode layer, a multi-quantum well light-emitting layer, a pAlGaN layer with Al component ratio being a preset ratio, a second metal electrode layer and a PGaN layer which are sequentially stacked from a substrate;
the area of the multiple quantum well light-emitting layer is the same as that of the pAlGaN layer and is smaller than that of the nAlGaN layer;
the area of the PGaN layer is smaller than that of the pAlGaN layer;
the first metal electrode layer and the nAlGaN layer form ohmic contact;
the second metal electrode layer comprises a first P electrode and a second P electrode, and the first P electrode is connected with the second P electrode or not connected with the second P electrode;
the first P electrode and the pAlGaN layer form ohmic contact, and the second P electrode and the PGaN layer form ohmic contact.
Preferably, part or all of the pGaN layer is covered with the second P electrode.
Preferably, the first and second P-electrodes are of the same composition, and/or of the same thickness.
Preferably, the first and second P-electrodes differ in composition, and/or in thickness.
Preferably, the electrode metal layers of the first metal electrode layer, the first P-electrode and the second P-electrode are all single-layer or multi-layer.
Preferably, the area of the pGaN layer occupies 10 to 80% of the area of the substrate.
Preferably, the AlN buffer layer has a first predetermined thickness of 2 to 3 μm.
Preferably, the first metal electrode layer covers a portion of the nAlGaN layer which is not covered by the multiple quantum well light emitting layer.
Preferably, the thickness of the nAlGaN layer is a second preset thickness which is 1 to 3 μm.
Preferably, the nAlGaN layer is doped with S with a preset concentration range in the growth process i And (4) elements.
Preferably, the pGaN layer has a circular or polygonal shape.
In the growth of the UVC LED epitaxial layer, processing methods such as a vapor phase epitaxy growth technology MOCVD, a Laser Lift Off technology (LLO), surface etching and the like are adopted to grow AlN, AlGaN, nAlGaN, an active layer, pAlGaN and pGaN on a substrate in sequence. Particularly, p-type metal electrode layers which are not on the same horizontal plane are deposited on the pAlGaN layer and the pGaN layer, and heat treatment is carried out on the generated p-type metal electrode layers in the preparation process so as to ensure that ohmic contact is formed. In the UVC LED structure, the erosion rate control layer is inserted between the generated pGaN and pAlGaN layers, so that part of the pGaN layer is effectively removed, the pAlGaN layer in the UVC LED structure is in ohmic contact with the metal electrode layer on the pAlGaN layer, and the pGaN layer is in ohmic contact with the metal electrode layer on the pGaN layer, and the light-emitting efficiency is further improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention.
Fig. 1 is a schematic cross-sectional view of an ultraviolet led structure according to an embodiment of the present invention.
Fig. 2 is a schematic perspective view of a light emitting diode according to an embodiment of the invention.
Fig. 3 is a schematic view of a light extraction direction of the led according to the embodiment of the invention.
FIG. 4 is a schematic diagram illustrating a heat treatment process for a metal layer according to an embodiment of the present invention.
Detailed Description
Various exemplary embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be noted that: the relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise.
Meanwhile, it should be understood that the sizes of the respective portions shown in the drawings are not drawn in an actual proportional relationship for the convenience of description.
The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments and the accompanying drawings.
Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate.
In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, further discussion thereof is not required in subsequent figures.
In a first embodiment, as shown in fig. 1, a cross-sectional view of an ultraviolet light emitting diode (UVC LED) structure provided in this embodiment is shown, where the UVC LED structure includes a substrate and an epitaxial layer grown on the substrate;
the epitaxial layer comprises an AlN buffer layer, an AlGaN layer, a nAlGaN layer, a first metal electrode layer, a multi-quantum well light-emitting layer, a pAlGaN layer with an Al component ratio x being a preset value, a second metal electrode layer and a PGaN layer which are sequentially stacked from the substrate;
the area of a multi-quantum well light-emitting layer (MQW) is the same as that of the pAlGaN layer and smaller than that of the nAlGaN layer, and the edge of the multi-quantum well light-emitting layer is aligned with three sides of the nAlGaN layer;
the area of the PGaN layer is smaller than that of the pAlGaN layer, and the edge of the PGaN layer is aligned with three edges of the pAlGaN layer;
the first metal electrode layer and the nAlGaN layer form ohmic contact and are positioned on the position, which is not covered by the multiple quantum well light-emitting layer, of the nAlGaN layer;
the second metal electrode layer can be divided into a first P electrode and a second P electrode, and the first P electrode and the second P electrode can be connected or not connected; and part or all of the surface area of the pGaN layer is covered by a second P electrode, the first P electrode is positioned on part or all of the surface area of the pAlGaN layer which is not covered by the pGaN layer, the first P electrode and the pAlGaN layer form ohmic contact, and the second P electrode and the PGaN layer form ohmic contact.
The substrate in the above structure may be formed of a substance excellent in thermal conductivity, or may be formed of a conductive substrate or an insulating substrate, such as a sapphire substrate (Al) 2 O 3 ) Any one of SiC, Si, GaAs, GaN, ZnO, GaP, InP, Ge, and Ga203, and the concavo-convex structure may be formed on the substrate.
The AlN buffer layer grows as the Al component decreases stepwise or exponentially at a certain ratio during the preparation process. Or, the AlN buffer layer can be grown by forming a pair of an AlGaN layer and an AlN layer having the same Al composition as the nAlGaN layer in a predetermined thickness or in two different thickness ranges (15 to 50) and repeatedly growing the pair of AlGaN layers and AlN layers 5 to 100 times.
The nAlGaN layer has a thickness of 1-3 um for efficient electron transfer, wherein S i The impurity concentration of (a) is in the range of 1e19 to 1e 21.
The AI composition ratio x in the pAlxGaN layer is in the range of 0.5< x.ltoreq.1, which can also be used as the Al composition ratio in the growth of the AlN buffer layer.
During the growth of the pGaN layer and the pAlxGaN layer, Be, Mg, Ca, Sr, Si, C, Ge, Sn and other components can Be used as impurities.
As can be seen from the sectional view fig. 1 and the perspective structure diagram fig. 2 of the ultraviolet light emitting diode structure in the embodiment of the present invention, the metal electrode layer of the structure of the present invention includes a first metal electrode layer on the nAlGaN layer, and a second metal electrode layer composed of a first p-electrode on the pAlGaN and a second p-electrode on the pGaN, wherein the first metal electrode layer covers a portion of the nAlGaN layer which is not covered by the multiple quantum well light emitting layer (active layer), the first p-electrode and the second p-electrode cover all or part of the area of the pGaN layer or the pAlGaN layer, and the two p-electrodes may be connected together or not connected; the first P electrode and the second P electrode have the same composition and/or the same thickness; the compositions, and/or the thicknesses of the first P electrode and the second P electrode can also be different;
in some embodiments, any one of the three metal electrode layers may form a single layer or a plurality of layers, and the metal forming the metal electrode layer may include at least one of Cu, Ni, Ti — W, Cr, W, Pt, V, Fe, and Mo species.
The growth of the epitaxial layer of the UVC LED light emitting structure in this embodiment can be formed by a Metal Organic Chemical Deposition (MOCVD), a Chemical Deposition (CVD), a Plasma-Enhanced Chemical Deposition (PECVD), a Molecular Beam growth (MBE), a Hydride Vapor Phase growth (HVPE), or the like.
In some embodiments, the area of the pGaN layer accounts for 10 to 80% of the surface area of the largest layer component in the UVC LED structure, and the area of the sapphire substrate is taken as the largest area of the whole UVC LED structure in this embodiment.
In some embodiments, the AlN buffer layer has a first predetermined thickness, preferably a first predetermined thickness of 2 μm to 3 μm.
In some embodiments, the nAlGaN layer is doped with Si elements in a predetermined concentration range, such as 1e 19-1 e21, during growth.
In some embodiments, the pGaN layer is circular in shape or an angular polygon of arbitrary shape.
The preparation method of the UVC LED structure in the embodiment comprises the following steps:
performing MOCVD at high temperature (preferably more than 1200 deg.C) on sapphire (Al) 2 O 3 ) On the substrate, TMAI (trimethyl aluminum) and ammonia (NH) are used 3 ) And growing an AlN layer with the thickness of 2-3 um.
Then, 80% of Al is grown by using any one of the following methods 80 And a GaN layer.
(1) Growing Al by gradually increasing Ga method 80 And a GaN layer. When an AlN layer is grown, an AlN layer having no Ga is grown first, and the AlN layer is grown while defining [ the molar concentration ratio of Ga + the molar concentration ratio of Al is 100%]The amount of Ga is gradually increased so that the molar concentration ratio of Ga becomes 20% of the total composition.
(2) Growth of Al using Superlattice mode 80 And a GaN layer. Mixing AlN and Al x GaN (here 0)<x<0.2) as a pair, 5 to 30 growths were carried out, in which case each layer used had a thickness of 0<AlNor Al x GaN<0.1 um. Then Al is added 80 The thickness of the GaN layer was grown to 0<Al 80 The thickness of GaN is less than or equal to 0.5 um.
(3) Mixing AlN and Al 80 GaN grows in a superlattice manner. The thickness of each layer in the method (2), AlN and Al being superimposed 80 The number of GaN layers is within 1-100,the final layer does not require Al as generated in method (2) 80 As thick as the GaN layer, Al thus grown 80 GaN can be doped with SiH 4 Grow into nAl 80 GaN layer, now growing nAl 80 The thickness of the GaN layer is between 1um and 3 um.
nAl grown as described above 80 And continuously growing an MQW active layer on the GaN layer, wherein the active layer is composed of a well layer which is combined with the electron holes to emit light and a barrier layer which induces the electron hole combination, and the number of the active layer is 3-6. The Al component of the AlGaN layer used in the well layer is 5% to 20% higher than that of the Al component used in the barrier layer. In addition, the thickness of the well layer is between
Between, the barrier layer is between
In the meantime.
And then growing the pAlGaN layer which plays a role of an electron blocking layer. The pGaN layer was removed using pAlGaN or the difference in etch rate of pAlN and pGaN. The higher the AI content (50% or more) of the AlGaN layer, the slower the etch rate compared to the etching of GaN, while the shorter the wavelength of the UVC LED, the higher the AI content of pAlGaN, so only a portion of the pGaN layer can be effectively removed by wet or dry etching techniques.
The final grown structure is etched in an epitaxial stepper, specifically with a photoresist covering the pGaN layer that should remain, using a conventional combination of dry and wet etching. In the etching, the part except the part to be covered by the n-type metal electrode layer is covered by the photoresist and then etched again by the wet etching technique until the n-type metal electrode nAlGaN layer is leaked. Then, in the growth of the pAlGaN layer, for better performing the function of the pAlGaN layer, the common dopant Mg is replaced by Cp 2 Mg, and the final thickness of the pAlGaN layer after replacement is 0.1 um-0.5 um. After the palGaN layer grows, the growth temperature is reduced by about 1000 ℃, so that the pGaN layer continues to grow.
After etching, the material for forming the n electrode and the material for forming the P electrode are respectively used for generating metal electrodes by using an electron beam evaporation coater (E-beam) and a magnetron sputtering coater, wherein the material for forming the electrodes is at least one of Cu, Ni, Ti, Ti-W, Cr, W, Pt, V, Fe, Mo and the like. After the two P-electrode layers constituting the second metal layer are formed, heat treatment is further performed at 300 to 800 degrees to reduce the contact resistance between the metal layer and the pGaN layer or between the metal layer and the nGaN layer, so that the metal layer and the pAlGaN layer are more preferably contacted. The heat treatment temperature of the metal layer may be adjusted according to the procedure shown in fig. 4.
The UVC LED structure provided by the invention can be prepared according to the method, and has the advantages that:
since the pAlGaN layer and the pGaN layer both form ohmic contacts in this structure, both layers can function as an effective p-type semiconductor layer. If the UVC LED structure of this embodiment is fabricated by the reverse bonding method, the metal electrode layer on the pAlGaN layer is reflected and injected with holes, and the metal layer on the pGaN layer acts as an excessive hole supply layer, so that the increase of the light extraction rate due to the increase of the reflectance and the increase of the light quantity due to the increase of the hole injection rate can be satisfied simultaneously with the decrease of the operating voltage of the UVC LED, and the specific light extraction direction is shown in fig. 3.
The above description is only exemplary of the present invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and scope of the present invention should be included in the present invention.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in the process, method, article, or apparatus that comprises the element.
Claims (11)
1. The ultraviolet light-emitting diode structure is characterized by comprising a substrate and an epitaxial layer grown on the substrate;
the epitaxial layer comprises an AlN buffer layer, an AlGaN layer, a nAlGaN layer, a first metal electrode layer, a multi-quantum well light-emitting layer, a pAlGaN layer with Al component ratio being a preset ratio, a second metal electrode layer and a PGaN layer which are sequentially stacked from a substrate;
the area of the multiple quantum well light-emitting layer is the same as that of the pAlGaN layer and is smaller than that of the nAlGaN layer;
the area of the PGaN layer is smaller than that of the pAlGaN layer;
the first metal electrode layer and the nAlGaN layer form ohmic contact;
the second metal electrode layer comprises a first P electrode and a second P electrode, and the first P electrode is connected with the second P electrode or not connected with the second P electrode;
the second P electrode and the PGaN layer form ohmic contact;
the first P electrode forms an ohmic contact with a portion of the pAlGaN layer not covered by the PGaN layer.
2. The UV LED structure of claim 1, wherein part or all of the pGaN layer is covered by the second P-electrode.
3. The UV LED structure of claim 1, wherein the first P electrode and the second P electrode are the same composition and/or thickness.
4. The UV LED structure of claim 1, wherein the first P-electrode and the second P-electrode are different in composition and/or thickness.
5. The UV LED structure of claim 1, wherein the electrode metal layers of the first metal electrode layer, the first P electrode and the second P electrode are all single-layered or multi-layered.
6. The UV LED structure of claim 1, wherein the pGaN layer has an area of 10-80% of the area of the substrate.
7. The UV LED structure of claim 1, wherein the AlN buffer layer has a first predetermined thickness.
8. The uv led structure of claim 1, wherein said first metal electrode layer covers the portion of said naclgan layer not covered by said multiple quantum well light emitting layer.
9. The UV LED structure of claim 1, wherein the nAIGaN layer has a second predetermined thickness.
10. The UV LED structure of claim 1, wherein the nAIGaN layer is doped with S in a predetermined concentration range during growth i And (4) elements.
11. The UV LED structure of claim 1, wherein the pGaN layer has a shape comprising a circle or a polygon.
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| CN1487603A (en) * | 2002-09-30 | 2004-04-07 | 中国科学院物理研究所 | Multiple quantum well structure and LED of the structure |
| CN102544298A (en) * | 2012-02-07 | 2012-07-04 | 厦门大学 | Deep-ultraviolet light emitting diode capable of effectively improving external quantum efficiency and method for preparing deep-ultraviolet light emitting diode |
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