CN110690327B - Preparation method of high-brightness purple light LED chip and LED chip - Google Patents
Preparation method of high-brightness purple light LED chip and LED chip Download PDFInfo
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- CN110690327B CN110690327B CN201911108379.7A CN201911108379A CN110690327B CN 110690327 B CN110690327 B CN 110690327B CN 201911108379 A CN201911108379 A CN 201911108379A CN 110690327 B CN110690327 B CN 110690327B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0075—Processes for devices with an active region comprising only III-V compounds comprising nitride compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/20—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 particular shape, e.g. curved or truncated substrate
- H01L33/22—Roughened surfaces, e.g. at the interface between epitaxial layers
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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
- H01L33/26—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 discloses a preparation method of a high-brightness purple light LED chip, which comprises the following steps: providing a substrate and forming an epitaxial layer; performing MESA etching on the epitaxial layer to form a hole penetrating through the first semiconductor layer; sequentially carrying out dry etching and wet etching on the side wall of the hole to form a secondary rough surface; forming a first electrode in the hole, and forming a second electrode in the second semiconductor layer; and splitting the substrate to obtain a high-brightness purple light LED chip finished product. Correspondingly, the invention also provides a purple light LED chip with high brightness; according to the invention, through the two-time etching process, the secondary rough surface is formed, so that the light extraction efficiency can be effectively improved, the light extraction efficiency is increased, and the brightness of the purple light LED chip is improved.
Description
Technical Field
The invention relates to the technical field of light emitting diodes, in particular to a preparation method of a high-brightness purple light LED chip and the LED chip.
Background
The purple light LED is a novel LED chip, the light-emitting wavelength of the purple light LED is 260-400 nm, and the wavelength of the purple light LED is shorter than that of a common blue-green light LED. The purple light LED is closer to sunlight, the sleep quality of a human body cannot be influenced like blue light, and the myopia problem is caused, so that the purple light LED has wide application prospect.
The existing purple light LED chip is mostly made of GaN-based semiconductors, but the refraction coefficient of a GaN material is large, so that the light extraction angle is small, the light extraction efficiency is greatly reduced, and the brightness of the purple light LED chip is reduced; especially, the wavelength of the purple light is shorter, so that the total reflection effect is more obvious, and the light extraction efficiency is lower.
In current blue-green light LED chip, in order to promote its light extraction efficiency, can carry out the alligatoring to its lateral wall usually, nevertheless because blue light LED chip wavelength is longer, once alligatoring can, need not to carry out further alligatoring.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a high-brightness purple light LED chip, and the prepared purple light LED chip has high light extraction efficiency and high brightness.
The invention also aims to provide a high-brightness purple light LED chip.
In order to solve the above technical problems, the present invention provides a method for preparing a high-brightness violet LED chip, comprising:
(1) providing a substrate, and forming an epitaxial layer on the substrate, wherein the epitaxial layer sequentially comprises a first semiconductor layer, an active layer and a second semiconductor layer;
(2) performing MESA etching on the epitaxial layer to form a plurality of holes penetrating through the first semiconductor layer;
(3) carrying out dry etching on the side wall of the hole to form a primary rough surface;
(4) carrying out wet etching on the primary rough surface to form a secondary rough surface;
(5) forming a first electrode in the hole, and forming a second electrode on the second semiconductor layer; and splitting the substrate to obtain a high-brightness purple light LED chip finished product.
As an improvement of the technical proposal, in the step (3), SiO is used2、SiNxAnd taking Ni or Pt as a mask, and etching for 10-15 minutes by adopting ICP (inductively coupled plasma) to form the primary rough surface.
As an improvement of the technical proposal, in the step (4), the primary rough surface is put on KOH or H3PO4Etching in the solution for 30-60 min; and in the etching process, ultraviolet irradiation is adopted to form the secondary rough surface.
As an improvement of the technical scheme, the wavelength of the ultraviolet light is less than or equal to 400 nm; the etching temperature is more than or equal to 50 ℃, KOH or H3PO4The mass concentration of the solution is more than or equal to 50 percent.
As an improvement of the above technical solution, the primary rough surface is provided with a plurality of first protrusions, and the first protrusions are in a stripe shape.
As an improvement of the above technical scheme, the secondary rough surface is provided with a plurality of second protrusions, and the second protrusions are circular, oval or fish scale-shaped; and a plurality of third bosses are arranged on the second bosses, and the third bosses are granular.
As an improvement of the technical scheme, the roughness of the secondary rough surface is more than or equal to 3.2 mu m.
As an improvement of the technical scheme, in the step (4), the etching depth is 100-500 nm.
As an improvement of the technical scheme, the step (5) comprises the following steps:
5.1) forming a transparent conductive layer on the second semiconductor layer;
(5.2) forming a second electrode on the transparent conductive layer, and forming a first electrode in the hole;
(5.3) forming a passivation layer on the transparent conductive layer, the first electrode, the second electrode and the epitaxial layer, and etching to expose the first electrode and the second electrode;
and (5.4) splitting to obtain a high-brightness purple light LED chip finished product.
Correspondingly, the invention also discloses a high-brightness purple light LED chip prepared by the preparation method.
The implementation of the invention has the following beneficial effects:
1. according to the high-brightness purple light LED chip provided by the invention, the secondary rough surfaces are arranged on the edges of the first semiconductor layer, the second semiconductor layer and the active layer, so that the light extraction efficiency can be effectively improved, the light extraction efficiency is increased, and the brightness of the purple light LED chip is improved.
2. According to the high-brightness purple light LED chip provided by the invention, the secondary rough surfaces are arranged on the edges of the first semiconductor layer, the second semiconductor layer and the active layer, so that Ga dangling bonds on the side wall of the hole after MESA etching can be effectively eliminated, and the problem of side leakage of the purple light LED is solved.
3. According to the invention, through the matching of dry etching and wet etching, a coarsening structure is further formed on the smooth side wall formed by one-time etching, the coarsening effect (which can have a specific shape) of the coarsening upper belt is shown, and the brightness of the purple light LED chip is further improved.
Drawings
FIG. 1 is a flow chart of a method for manufacturing a high-brightness purple LED chip according to the present invention;
FIG. 2 is an electron micrograph of a primary matte surface;
FIG. 3 is an electron microscope photograph of a secondary rough surface;
FIG. 4 is another electron micrograph of a secondary asperity;
FIG. 5 is a schematic structural diagram of a high-brightness purple LED chip according to the present invention;
fig. 6 is a schematic structural diagram of a high-brightness LED chip according to another embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings. It is only noted that the invention is intended to be limited to the specific forms set forth herein, including any reference to the drawings, as well as any other specific forms of embodiments of the invention.
Referring to fig. 1, the present invention provides a method for preparing a high-brightness violet LED chip, which comprises the following steps:
s1: providing a substrate, and forming an epitaxial layer on the substrate;
the substrate may be sapphire, but is not limited thereto.
The epitaxial layer comprises a first semiconductor layer, an active layer and a second semiconductor layer; the first semiconductor layer and the second semiconductor layer are both gallium nitride-based semiconductor layers, and the active layer is a gallium nitride-based active layer; in addition, the materials of the first semiconductor layer, the second semiconductor layer and the active layer provided by the present application may also be other materials, and the present application is not particularly limited.
S2: performing MESA etching on the epitaxial layer to form a plurality of holes penetrating through the first semiconductor layer;
specifically, the epitaxial layer is etched by using ICP or RIE etching equipment to form a hole penetrating through to the first semiconductor layer. It should be noted that the MESA etching may adopt a common wet etching or dry etching process, and the present invention is not limited in particular.
S3: carrying out dry etching on the side wall of the hole to form a primary rough surface on the side wall of the hole;
the side wall of the hole may be dry etched by using plasma etching (ICP), Reactive Ion Etching (RIE), Reactive Ion Beam Etching (RIBE), but is not limited thereto. The dry etching has higher etching speed than the wet etching, and the etching shape has high controllability. The crystal form of the GaN can be quickly etched by adopting dry etching, and a good foundation is provided for subsequent secondary coarsening.
Preferably, etching the side wall of the hole by using a plasma etching device (ICP); in particular, SiO is used2、SiNxAnd taking Ni or Pt as a mask, and etching for 10-15 minutes by adopting ICP (inductively coupled plasma) to form a primary rough surface.
Specifically, after the etching process, referring to fig. 2, a plurality of smooth first protrusions are formed on the sidewall of the hole; the first protrusion is stripe, but not limited thereto. The first protruding part in the shape can improve the light extraction efficiency of the purple light LED chip and improve the brightness of the purple light LED chip.
S4: carrying out wet etching on the primary rough surface to form a secondary rough surface;
wherein KOH or H is used3PO4And carrying out wet etching on the primary rough surface by using the solution, wherein the etching time is 30-60 min, and ultraviolet irradiation is adopted in the etching process. The ultraviolet light can effectively activate the tip of the first rough convex part which is roughened for the first time, and the roughness of the rough surface for the second time is improved. Wherein the depth of the secondary etching is 100-500 nm, preferably 100-300 nm.
Wherein, KOH solution or H3PO4The mass concentration of the solution is more than 50 percent, and the wavelength of ultraviolet lightThe thickness is not more than 400nm, the etching temperature is not less than 50 ℃, and further optimization is carried out, wherein the etching temperature is 50-80 ℃; under this condition, the primary rough surface can be effectively roughened.
After the secondary roughening process, the primary rough surface is roughened again, a roughened upper-belt roughened structure is formed (shown in fig. 3 and 4), and the light extraction efficiency of the violet LED is greatly improved. Meanwhile, the secondary rough surface can effectively reduce Ga dangling bonds on the side wall of the hole, and the problem of electric leakage of the side edge of the purple light LED is solved.
Specifically, the secondary rough surface is provided with a plurality of second protruding parts, and the second protruding parts are circular, oval or fish scale-shaped; the side wall of the second bulge is also provided with a plurality of third bulges, and the third bulges are granular. Preferably, the second protruding part is in a fish scale shape, and the third protruding part is in a granular shape (fig. 4); the light extraction efficiency of the purple light LED can be improved and the brightness of the purple light LED can be improved through the secondary rough surface with the structure; and Ga dangling bonds on the side wall of the hole can be reduced, and the problem of electric leakage of the side edge of the purple light LED is solved.
It should be noted that, most of the existing blue-green LED is roughened once, and wet roughening is generally adopted, that is, after MESA etching, the LED chip is immersed in a solution for roughening. Therefore, the invention uses a process of roughening twice, firstly adopts dry etching to etch a large stripe-shaped outline, and then adopts wet etching to further decompose (micro-roughen) the stripe-shaped bulge to form a granular small structure on the stripe-shaped bulge, so that a structure with roughening on the upper surface is formed, the light extraction efficiency of the violet LED is improved, and Ga dangling bonds on the side wall of the hole are reduced. The primary dry etching has high precision and high etching speed, and can rapidly etch the GaN crystal form to form a primary etching shape with larger size; the secondary wet etching is mainly to roughen the surface of the shape obtained by the primary etching so as to obtain a structure with a roughened upper zone. If the long-time dry etching is adopted, the micro-coarsening structure cannot be prepared, the long-time dry etching is easy to cause side damage, and the Ga dangling bond is greatly increased; if the wet etching is carried out for a long time, only a micro-roughening structure can be obtained, and the use requirement cannot be met; if the procedure of wet etching and then dry etching is adopted, a structure with coarsened upper strips cannot be formed, and the sidewall Ga dangling bonds left by the dry etching cannot be eliminated; therefore, the above three processes cannot simultaneously achieve the effects of improving the light extraction efficiency and eliminating the sidewall Ga dangling bond.
S5: and forming a first electrode in the hole, forming a second electrode on the second semiconductor layer, and splitting to obtain a high-brightness purple light LED finished product.
Preferably, step S5 includes:
s51: forming a transparent conductive layer on the second semiconductor layer, and etching the transparent conductive layer to enable the width of the transparent conductive layer to be smaller than that of the second semiconductor layer;
s52: forming a first electrode in the hole, and forming a second electrode on the second semiconductor layer;
s53: forming a passivation layer on the first semiconductor layer, the first electrode, the transparent conductive layer, the second electrode and the second semiconductor layer, and etching to expose the first electrode and the second electrode;
s54: grinding to reduce the thickness of the substrate;
s55: and scribing the substrate by adopting laser, and cleaving by using a steel cleaver to form crystal grains, thereby obtaining a high-luminous-efficiency purple light LED chip finished product.
Correspondingly, the invention also discloses a high-brightness purple light LED chip which is prepared by adopting the method. In particular, see fig. 5, which includes a substrate 1; the epitaxial layer 2 is arranged on the surface of the substrate 1, and the epitaxial layer 2 comprises a first semiconductor layer 21, an active layer 22 and a second semiconductor layer 23; a first electrode 3 is arranged on the first semiconductor layer 21, and a second electrode 4 is arranged on the second semiconductor layer 23; wherein, the second rough surface 5 is provided on the sidewall of the first semiconductor layer 21, the active layer sidewall 22 and the second semiconductor layer 23 adjacent to the second electrode 23. The secondary rough surface 5 can effectively improve the light emitting effect, and further plays a role in improving the brightness of the purple light LED chip.
Specifically, the secondary rough surface 5 is formed by a secondary etching process of firstly performing dry etching and then performing wet etching; specifically, after MESA etching, a hole is formed; and then, carrying out dry etching and wet etching on the side wall of the hole in sequence to form a secondary rough surface 5.
It should be noted that, during the MESA etching and the one-time dry etching, Ga dangling bonds are easily generated on the side wall of the hole, and when in use, the reverse leakage problem is easily caused; the invention effectively repairs the dangling bond on the side surface through the secondary rough surface 5, and solves the problem of electric leakage on the side surface of the LED chip.
Specifically, in this embodiment, the second rough surface 5 is provided with a plurality of second protruding portions 51, and the second protruding portions 51 can effectively improve the light-lifting efficiency and improve the brightness of the LED chip. Further, a plurality of third projecting portions 52 are provided on the second projecting portion 51; the third protruding portion 52 is a micro-roughened structure, which can further improve the light extraction efficiency.
Specifically, the second protrusion 51 has a circular, oval or fish scale shape, but is not limited thereto. Specifically, as shown in fig. 3, in the present embodiment, the second protrusion 51 is in a fish scale shape; the second convex part 51 in the shape of the fish scale has higher light extraction efficiency, and the brightness of the LED chip is improved. In another embodiment of the present invention, the second protruding portion 51 is circular, and the circular second protruding portion 51 also has high light extraction efficiency, which can effectively improve the brightness of the LED chip.
Further, in order to fully exert the functions of improving the brightness and eliminating side leakage of the secondary rough surface 5, the roughness of the secondary rough surface 5 should be more than or equal to 3.2 μm, and when the roughness of the secondary rough surface 5 is less than 3.2 μm, a good refraction effect on emitted light cannot be formed, namely, the light extraction efficiency cannot be improved; meanwhile, the repair effect on the Ga dangling bond on the side surface is weak. Preferably, the roughness of the rough surface is 3.2-100 μm; further preferably 5 to 20 μm; the secondary rough surface 5 in this range has the most excellent effect.
Specifically, referring to fig. 6, in another embodiment of the present invention, the LED chip further includes a transparent conductive layer 6 disposed on the surface of the second semiconductor layer 23, which is made of ITO, IZO, GZO, or the like, but is not limited thereto; the transparent conductive layer 6 can enhance current distribution and improve the brightness of the LED. Furthermore, the width of the transparent conducting layer 6 is smaller than that of the second semiconductor layer 23, the structural design can effectively reduce the current distribution of the side wall of the second semiconductor layer 23, the side wall of the active layer 22 and the side wall of the first semiconductor layer 21, and the side surface leakage problem of the LED chip is completely eliminated by cooperating with the secondary rough surface 5.
Specifically, referring to fig. 6, in another embodiment of the present invention, the LED chip further includes a barrier layer 7; the barrier layer 7 covers the surface and the sidewall of the first semiconductor layer 21, the surface and the sidewall of the second semiconductor layer 22, the surface and the sidewall of the transparent conductive layer 6, the surface and the sidewall of the first electrode 3, the surface and the sidewall of the second electrode 4, and the sidewall of the active layer 22. The surfaces of the first electrode 3 and the second electrode 4 are exposed out of the barrier layer 7 through etching. The barrier layer 7 can effectively protect the LED chip. The barrier layer 7 is made of photoresist and SiO2、SiNxOr Ni.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (5)
1. A preparation method of a high-brightness purple light LED chip is characterized by comprising the following steps:
(1) providing a substrate, and forming an epitaxial layer on the substrate, wherein the epitaxial layer sequentially comprises a first semiconductor layer, an active layer and a second semiconductor layer;
(2) performing MESA etching on the epitaxial layer to form a plurality of holes penetrating through the first semiconductor layer;
(3) carrying out dry etching on the side wall of the hole to form a primary rough surface; the primary rough surface is provided with a plurality of first protruding parts, and the first protruding parts are in stripe shapes;
(4) carrying out wet etching on the primary rough surface to form a secondary rough surface, wherein the roughness of the secondary rough surface is more than or equal to 3.2 mu m; the secondary rough surface is provided with a plurality of second protruding parts, and the second protruding parts are circular, oval or fish scale-shaped; a plurality of third protruding parts are arranged on the second protruding parts, and the third protruding parts are granular;
(5) forming a first electrode in the hole, and forming a second electrode on the second semiconductor layer; splitting the substrate to obtain a high-brightness purple light LED chip finished product;
in the step (4), the primary rough surface is placed in KOH or H3PO4Etching in the solution for 30-60 min; and in the etching process, ultraviolet irradiation is adopted to form the secondary rough surface, and the etching depth is 100-500 nm.
2. The method of claim 1, wherein in step (3), SiO is used as the material of the high-brightness purple LED chip2、SiNxAnd taking Ni or Pt as a mask, and etching for 10-15 minutes by adopting ICP (inductively coupled plasma) to form the primary rough surface.
3. The method according to claim 1, wherein the wavelength of the ultraviolet light is 400nm or less; the etching temperature is more than or equal to 50 ℃, KOH or H3PO4The mass concentration of the solution is more than or equal to 50 percent.
4. The method of manufacturing a violet LED chip of high brightness according to claim 1, wherein the step (5) comprises:
(5.1) forming a transparent conductive layer on the second semiconductor layer;
(5.2) forming a second electrode on the transparent conductive layer, and forming a first electrode in the hole;
(5.3) forming a passivation layer on the transparent conductive layer, the first electrode, the second electrode and the epitaxial layer, and etching to expose the first electrode and the second electrode;
and (5.4) splitting to obtain a high-brightness purple light LED chip finished product.
5. A high-brightness purple light LED chip prepared by the preparation method of any one of claims 1 to 4.
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