TWI443870B - Vertical light emitting diode and its manufacturing method - Google Patents

Description

Vertical light-emitting diode and manufacturing method thereof

The invention relates to a vertical light-emitting diode and a manufacturing method thereof, in particular to a vertical light-emitting diode with high power and large size and a manufacturing method thereof.

Since the 1960s, the advantages of low power consumption and long-lasting luminescence of LEDs have gradually replaced the use of indicators or light sources for lighting or various electrical appliances in daily life. What's more, the development of light-emitting diodes towards multi-color and high brightness has been applied to large outdoor display billboards or traffic signs.

However, the light-emitting diode 100 used in the prior art has a structure as shown in FIG. 1, and the positive electrode 107 and the negative electrode 108 are all on the same side. Moreover, the substrate 101 (such as sapphire) used in the conventional light-emitting diode is not electrically conductive, so the current must be converted from a vertical downstream to a horizontal cross-flow in the semiconductor layer 102, so that the current is concentrated in the inner bend, which cannot be completely The electron layer and the hole layer of the PN interface are used to reduce luminous efficiency. In addition, the foregoing current may generate a hot spot at the concentration of the semiconductor layer 102, causing a defect in the crystal lattice in the semiconductor layer 102, thereby affecting the service life of the light-emitting diode 100; or only reducing the power to avoid the occurrence of hot spots. This reduces the luminous effect of the light-emitting diode 100 and limits its use.

The problem of causing current turning in the light-emitting diode cannot be improved by the improvement of the package design. For example, even if the light-emitting diode is fabricated by flip chip, it is impossible to avoid hot spots, cause lattice defects, affect luminous efficiency, and Loss of service life, etc.

Therefore, another vertical light-emitting diode is produced by making electrodes on both sides of the light-emitting diode to improve the current direction. However, the vertical light-emitting diodes used today often use a tantalum carbide (SiC) substrate to grow gallium carbide. However, since the price of the SiC single crystal substrate is too high, it is generally replaced by a substrate such as Si or a metal, and the epitaxial layer is bonded with a metal such as gold-gold, gold-tin-gold-tin, or indium-indium. However, since the difference in thermal expansion coefficient between the epitaxial layer and the metal substrate or the metal bonding layer is large, the yield of the light emitting diode is often poor in the subsequent stripping process.

Therefore, there is a need for a light-emitting diode having a high power, a good heat dissipation effect, and a large size, and a manufacturing method thereof.

To achieve the foregoing objective, the present invention provides a method of fabricating a vertical light emitting diode comprising the steps of: providing a substrate; forming a semiconductor layer on the substrate, the semiconductor layer having elements of Group II to VI a compound formed by forming a metal reflective layer to be bonded to the semiconductor layer; forming at least one intermediate layer and at least one type of drilled carbon layer; forming a composite material layer; removing the substrate; and forming a first electrode layer and A second electrode layer is disposed on one side of the semiconductor layer and the composite material layer; wherein at least one intermediate layer and at least one type of drilled carbon layer are stacked on one side of the metal reflective layer in a stacked manner.

According to the manufacturing method of the present invention, the manner in which the substrate is removed is not particularly limited as long as it does not cause the substrate to be removed, resulting in bending of each layer structure in the light-emitting diode due to interface stress. A preferred method of removal is to cause the substrate to be peeled off from the semiconductor layer by a laser.

In addition, according to the manufacturing method of the present invention, a semiconductor layer, a metal reflective layer, at least one intermediate layer, and at least one type of diamond-forming carbon layer may be selected according to a process, wherein a cathode arc, sputtering, steaming is preferably used. Deposited by plating, electroplating, electroless plating, or coating.

According to the manufacturing method of the present invention, the substrate may be a substrate of Al ₂ O ₃ (sapphire), Si, SiC, GaAs, GaP, AlP, GaN, C (graphite), hBN, or C (diamond); Or a substrate having at least one cation of a nitride of B, Al, Ga, In, Be, Mg, a phosphide, or an arsenide; the composition of the semiconductor layer may be Al ₂ O ₃ (sapphire), Si, SiC, GaAs, GaP, AlP, GaN, C (graphite), hBN, or C (diamond); or a nitride, phosphide, or arsenide of at least one cation of B, Al, Ga, In, Be, Mg; metal reflective layer It may be at least one selected from the group consisting of Ag, Al, Ni, Co, Pd, Pt, Au, Zn, Sn, Sb, Pb, Cu, CuAg, NiAg, and the foregoing metal alloy, and the thickness of the metal reflective layer There is no limitation, as long as the guiding light can be achieved and the luminous efficiency is increased, preferably 100-500 nm, and most preferably 200 nm.

According to the manufacturing method of the present invention, the material of the intermediate layer is selected to use a metal capable of reacting with carbon and capable of synthesizing a carbide former, and preferably includes at least one selected from the group consisting of Ti, V, and Cr. A material such as a group consisting of Zr, Nb, Mo, Hf, Ta, W, and an alloy of the foregoing metals. The thickness of the intermediate layer is not limited, and is preferably 50 to 500 nm, more preferably 100 nm.

According to the manufacturing method of the present invention, the diamond-like carbon layer is used to eliminate the waste heat generated by the light-emitting diode during light emission, and is quickly eliminated in a conductive manner, thereby prolonging the service life of the light-emitting diode.

According to the manufacturing method of the present invention, the composite material layer may comprise a composite material composed of at least one metal and diamond, and the diamond may be arranged in a single layer, a plurality of layers, or a randomly distributed cloth in the composite layer, wherein the diamond occupies a composite The total volume of the material layer is 25-60%, preferably 30-50%. The composition of the metal may be at least one selected from the group consisting of Cu, Ag, Co, Ni, W, Fe, Ti, Cr, and B; the diamond may be synthetic diamond grits, and the diamonds are The preferred particle size is from 1 μm to 1 mm.

According to the manufacturing method of the present invention, the thickness of the composite material layer is not particularly limited, and a thickness is preferably from 100 to 500 μm, more preferably 150 μm. In addition, the thermal expansion coefficient of the composite layer can be adjusted as needed to avoid bending or internal defects of the semiconductor layer of the light-emitting diode due to the interface stress during the manufacturing process, thereby reducing the yield of the product and increasing the production cost. Or a light attenuating effect; according to the manufacturing method according to the present invention, the composite layer preferably has a coefficient of thermal expansion of from 2 to 10 ppm/°C. Furthermore, according to the manufacturing method of the present invention, the method further comprises the step of polishing the surface of the composite material layer to Ra<1 μm, mainly to keep the peeling surface flat when the substrate and the light emitting diode structure are peeled off. The surface error is less than 1 mm.

According to the manufacturing method of the present invention, a transparent diamond-like carbon layer is further formed on one side of the semiconductor layer, and the function thereof mainly removes heat radiation (such as a phosphor powder layer) generated in the light-emitting diode quickly. Increase the efficiency of the square light and product cycle. As for the transparent diamond-like carbon layer, any deposition method may be used as desired, and it is preferably formed by plasma chemical vapor deposition (PECVD). In addition, the transparent diamond-like carbon layer may further include a hydrogen atom therein, and the content thereof may be about 15-40 atomic percent of the transparent diamond-like carbon layer, thereby increasing the heat-eliminating effect and the light-emitting diode. Luminous efficiency.

The invention also provides a method for manufacturing a vertical light-emitting diode, comprising the steps of: providing a substrate; forming a semiconductor layer on the substrate, the semiconductor layer having a compound composed of elements of Group II to VI; Forming a metal reflective layer to be bonded to the semiconductor layer; forming a composite material layer; removing the substrate; and forming a first electrode layer and a second electrode layer respectively disposed on the semiconductor layer and the composite One side of the material layer. As for the manufacturing method, the method steps and the structure of each layer (such as a substrate, a semiconductor layer, a metal reflective layer, a composite material layer, and a first electrode layer and a second electrode layer) are defined as described above.

Another object of the present invention is to provide a vertical light emitting diode comprising: a semiconductor layer having a compound composed of elements of Group II to VI; a metal reflective layer bonded to the semiconductor layer; At least one intermediate layer; at least one type of drilled carbon layer; a composite material layer; and a first electrode layer and a second electrode layer respectively disposed on one side of the semiconductor layer and the composite material layer; wherein at least one intermediate layer and At least one type of drilled carbon layer is stacked on one side of the metal reflective layer in a stacked manner.

A vertical light emitting diode according to the present invention, wherein the composition of the semiconductor layer may be Al ₂ O ₃ (sapphire), Si, SiC, GaAs, GaP, AlP, GaN, C (graphite), hBN, or C (diamond) Or at least one cation is a nitride, phosphide, or arsenide of B, Al, Ga, In, Be, Mg; the metal reflective layer may be at least one selected from the group consisting of Ag, Al, Ni, Co, Pd, Pt, Au, Zn, Sn, Sb, Pb, Cu, CuAg, NiAg, and the foregoing metal alloy group, and the thickness of the metal reflective layer is not limited, as long as the guiding light can be achieved and the luminous efficiency is increased, preferably It can be 100-500 nm, preferably 200 nm.

According to the vertical light-emitting diode of the present invention, the material of the intermediate layer is selected to use a metal capable of reacting with carbon and capable of synthesizing a carbide former, preferably including at least one selected from the group consisting of Ti. A material such as a group consisting of V, Cr, Zr, Nb, Mo, Hf, Ta, W, and an alloy of the foregoing metals. The thickness of the intermediate layer is not limited, and is preferably 50 to 500 nm, more preferably 100 nm.

According to the vertical light-emitting diode of the present invention, the diamond-like carbon layer is used to eliminate the waste heat generated by the light-emitting diode during light emission, and is quickly removed in a conductive manner, thereby prolonging the service life of the light-emitting diode.

According to the vertical light-emitting diode of the present invention, the composite material layer may comprise a composite material composed of at least one metal and diamond, and the diamond may be arranged in a single layer, a plurality of layers, or a randomly distributed cloth in the composite layer, wherein The diamond accounts for about 25-60% of the total volume of the composite layer, preferably 30-50%. The composition of the metal may be at least one selected from the group consisting of Cu, Ag, Co, Ni, W, Fe, Ti, Cr, and B; the diamond may be synthetic diamond grits, and the diamonds are The preferred particle size is from 1 μm to 1 mm.

According to the vertical light-emitting diode of the present invention, the thickness of the composite material layer is not particularly limited, and a thickness is preferably from 100 to 500 μm, more preferably 150 μm. In addition, the thermal expansion coefficient of the composite layer can be adjusted as needed to avoid bending or internal defects of the semiconductor layer of the light-emitting diode due to the interface stress during the manufacturing process, thereby reducing the yield of the product and increasing the production cost. Or a light attenuating effect; according to the manufacturing method according to the present invention, the composite layer preferably has a coefficient of thermal expansion of from 2 to 10 ppm/°C. Further, according to the vertical light-emitting diode of the present invention, the surface of the composite material layer is polished to Ra < 1 μm.

The vertical light-emitting diode according to the present invention further comprises a transparent diamond-like carbon layer formed on one side of the semiconductor layer, the main function of which is to enable thermal radiation (such as a phosphor layer) generated in the light-emitting diode. Quickly eliminate, in order to increase the efficiency and product cycle. As for the transparent diamond-like carbon layer, any deposition method may be used as desired, and it is preferably formed by plasma chemical vapor deposition (PECVD). In addition, the transparent diamond-like carbon layer may further include a hydrogen atom therein, and the content thereof may be about 15-40 atomic percent of the transparent diamond-like carbon layer, thereby increasing the heat-eliminating effect and the light-emitting diode. Luminous efficiency.

According to still another object of the present invention, there is provided a vertical light emitting diode comprising: a semiconductor layer having a compound composed of elements of Group II to VI; and a metal reflective layer bonded to the semiconductor layer a composite material layer; and a first electrode layer and a second electrode layer respectively disposed on one side of the semiconductor layer and the composite material layer; wherein the composite material layer is directly at about 300 ° C with Au or Au-Sn Soft soldering is applied to the metal reflective layer or directly to high temperature bonding. As for the structure of the vertical light-emitting diode, the definition of each layer structure (such as a substrate, a semiconductor layer, a metal reflective layer, a composite material layer, and a first electrode layer and a second electrode layer) is as described above.

It can be seen from the above that the conventionally used light-emitting diodes are incident on the same side because both positive and negative electrodes are used, and since the substrate (such as sapphire) used in the conventional light-emitting diode is not electrically conductive, the current must be in the semiconductor layer. The vertical forward flow is converted into a horizontal cross flow, so that the current is concentrated in the inner bend, and the electron layer and the hole layer of the PN interface cannot be completely used, thereby reducing the luminous efficiency. In addition, the aforementioned current generates a hot spot at the concentration, causing a defect in the crystal lattice in the semiconductor layer, thus affecting the service life of the light-emitting diode. However, the vertical light-emitting diode according to the present invention and the manufacturing method thereof use not only a composite material layer composed of at least one metal and diamond, but also at least one intermediate layer and at least one type of drill carbon layer, and will be first The electrode layer and the second electrode layer are respectively disposed on both sides of the beam splitting diode structure. Therefore, the carbon fiber layer of the invention has high thermal conductivity, so as to quickly eliminate the waste heat generated when the light-emitting diode emits light, and the internal crystal lattice defect is not generated in the semiconductor layer due to uneven current density distribution. Problems such as light decay or service life.

Therefore, according to the light-emitting diode of the present invention and the method of manufacturing the same, a vertical light-emitting diode having a large size (>1 mm), a large current (>1 A/mm ² ), and a high power (>10 W) can be realized. It is better than paralleling a plurality of conventional light-emitting diodes that use current to bend current. According to the vertical light-emitting diode of the present invention and the method of manufacturing the same, the light-emitting efficiency is better to make it brighter, and the thermal conductivity of the carbon-like layer is excellent to eliminate the waste heat generated when the light is emitted, and to solve internal defects. More durable and so on.

Referring to FIG. 2E and FIG. 3, the vertical LED structure obtained by the manufacturing method of the present invention comprises a semiconductor layer 202 having a compound composed of elements of Group II to VI; a metal reflection. The layer 203 is combined with the semiconductor layer 202; at least one intermediate layer 204; at least one type of drilled carbon layer 205; a composite material layer 206; and a first electrode layer 207 which may be a negative electrode and a first electrode which may be a positive electrode The two electrode layers 208 are respectively disposed on one side of the semiconductor layer 202 and the composite material layer 206; wherein at least one intermediate layer 204 and at least one type of drilled carbon layer 205 are stacked on one side of the metal reflective layer in a stacked manner .

Hereinafter, a method of manufacturing the vertical light-emitting diode of the present invention will be described in detail:

Example 1

Referring to Figures 2A through 2E, a specific embodiment of the present invention for fabricating a vertical light-emitting diode is shown. First, as shown in FIG. 2A, a substrate 201 is provided. In the embodiment, the substrate 201 is a sapphire substrate, and Si, SiC, GaAs, GaP, AlP, GaN, and the like are selected according to the requirements of the process. C (graphite), hBN, C (diamond), or a substrate in which at least one cation is a nitride, phosphide, or arsenide of B, Al, Ga, In, Be, Mg. Next, as shown in FIG. 2B, a semiconductor layer 202 is formed on the substrate 201, and the semiconductor layer 202 has a compound composed of elements of Group II to VI, such as Al ₂ O ₃ (sapphire), Si, SiC, GaAs, GaP. , AlP, GaN, C (graphite), hBN, C (diamond), or at least one cation is a nitride, phosphide, or arsenide of B, Al, Ga, In, Be, Mg, in this embodiment GaN is used as the semiconductor layer 202. Thereafter, as shown in FIG. 2C, a metal reflective layer 203 is formed, which is deposited by a cathodic arc and bonded to the semiconductor layer 202. The metal reflective layer 203 may be Ag or Al, and other metal reflective layers 203 may be selected. The material may be Ni, Co, Pd, Pt, Au, Zn, Sn, Sb, Pb, Cu, CuAg, NiAg, or the foregoing metal alloy, and the thickness of the metal reflective layer 203 is not limited as long as the guiding light can be achieved. The luminous efficiency may be increased, preferably 100-500 nm, and the metal reflective layer 203 in the present embodiment is about 200 nm.

Next, as shown in FIG. 2D, an intermediate layer 204 and a type of drilled carbon layer 205 are sequentially formed by sputtering, wherein the material of the intermediate layer 204 is selected to be capable of reacting with carbon and capable of synthesizing carbonization. The metal of the material may preferably comprise at least one material selected from the group consisting of Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W, and alloys of the foregoing metals, in this embodiment. Titanium is used as the intermediate layer 204. As for the thickness of the intermediate layer 204, there is no limitation, preferably 50-500 nm, and the intermediate layer of this embodiment is about 100 nm. The thickness of the diamond-like carbon layer 205 is not particularly limited as long as a better heat dissipation effect can be achieved and the intermediate layer 204 can be tightly bonded, and the intermediate layer 204 and the diamond-like carbon layer 205 can be stacked on each other in a stacked manner. Further, the situation that the structure of each layer in the light-emitting diode is bent due to the interface stress is reduced, and the yield is lowered. The thickness of the diamond-like carbon layer 205 is preferably greater than 300 nm, and the embodiment has a thickness of about 500 nm or the like. The carbon layer 205 is drilled. In addition, a thinner intermediate layer 204 (about 60 nm) can be selectively formed on the upper diamond-like carbon layer 205 to form a structure as shown in FIG. 2D.

Finally, as shown in FIG. 2E, a composite material layer 206 is formed on the foregoing structure, and the substrate 201 is removed. Thereafter, a first electrode layer 207 and a second electrode layer 208 are formed, which are respectively disposed on the semiconductor layer 202 and One side of the composite layer 206. The composite material layer 206 may comprise a composite material composed of at least one metal and diamond, and the diamond may also be selectively arranged in a single layer, a plurality of layers, or a randomly distributed cloth in the composite layer. The diamond accounts for about 25-60% of the total volume of the composite layer 206, preferably in the proportion of 30-50% of the total volume of the composite layer used in this embodiment. The composition of the metal may be at least one selected from the group consisting of Cu, Ag, Co, Ni, W, Fe, Ti, Cr, and B. In this embodiment, metal nickel is used as the composition; the diamond may be synthesized. Synthetic diamond grits, and the preferred particle size of the diamond is 1 μm-1 mm. In other words, the composite layer 206 of the present embodiment is a nickel-diamond composite. As for the thickness of the composite material layer 206, which is preferably 100-500 μm, the thickness of the composite material layer 206 in the present embodiment is about 150 μm.

According to this embodiment, the substrate 201 is removed by peeling off the substrate from the semiconductor layer by a gas laser (KrF, wavelength about 248 nm). The method is not only relatively quick and simple, but also the vertical light-emitting diode structure prepared by the embodiment does not cause the substrate layer 201 to be removed due to the interface stress caused by the removal of the substrate 201. Causes bending. Furthermore, according to the embodiment, the step of polishing the surface of the composite material layer 206 to Ra<1 μm is mainly to prevent the flat surface of the peeling surface from being less than that when the substrate 201 and the light emitting diode structure are peeled off. 1 mm.

In addition, according to the manufacturing method of the embodiment, the semiconductor layer 202, the metal reflective layer 203, the intermediate layer 204, and the diamond-like carbon layer 205 may be formed according to a process, in which a cathode arc, sputtering, or the like may be used. Formed by evaporation, electroplating, electroless plating, coating, soldering, or deposition.

As mentioned above, the coefficient of thermal expansion of the composite material layer 206 can be adjusted as needed to avoid bending or internal defects of the semiconductor layer 202 of the light-emitting diode due to interface stress during the manufacturing process, thereby reducing the yield of the product. The production cost or the light attenuation effect is increased; the composite material layer 206 according to this embodiment has a thermal expansion coefficient of about 10 ppm/°C.

According to the manufacturing method of the embodiment, a transparent diamond-like carbon layer (not shown) may be further formed on one side of the semiconductor layer, and the main function thereof is to generate heat radiation (such as phosphor powder) generated in the light-emitting diode. Layer) can be quickly eliminated to increase luminous efficiency and product cycle. As for the transparent diamond-like carbon layer, any deposition method may be used as needed, for example, by plasma chemical vapor deposition (PECVD). In addition, the transparent diamond-like carbon layer may further include a hydrogen atom therein, and the content thereof may be about 15-40 atomic percent of the transparent diamond-like carbon layer, thereby increasing the heat-eliminating effect and the light-emitting diode. Luminous efficiency.

Example 2

The manufacturing method used in this embodiment is similar to that of the first embodiment. Therefore, the structure can also be directly referred to as FIG. 2E. The difference is that the metal reflective layer 203 (such as silver) is formed on the semiconductor layer by sputtering in the manufacturing process. On a 202 (such as GaN), a copper-diamond composite is used as the composite layer 206. Therefore, the composite material layer 206 according to the present embodiment has a coefficient of thermal expansion of about 5 ppm/°C. The structure and characteristics of the other layers are as defined in Embodiment 1.

Example 3

As shown in FIG. 3, the manufacturing method used in the present embodiment is similar to that of Embodiment 1 and Embodiment 2, except that the intermediate layer 304 and the diamond-like carbon layer 305 are sequentially stacked on each other in the manufacturing process, and the middle is stacked. The laminate structure of layer 304 and diamond-like carbon layer 305 has a total thickness of about 3 μm, and in the present embodiment a copper-nickel-diamond composite is used as composite layer 306. Therefore, according to the composite material layer 306 of the present embodiment, the coefficient of thermal expansion can be adjusted to about 2 to 10 ppm/° C. as required in the process. The structure and characteristics of the other layers are as defined in Embodiment 1.

Example 4

As shown in FIG. 4, the manufacturing method used in the present embodiment is similar to that of Embodiment 1 and Embodiment 2, except that in the present embodiment, the diamond-like carbon layer and the intermediate layer are not formed, but a first electrode is formed. 407 / semiconductor layer 402 / metal reflective layer 403 / composite material layer 406 / second electrode 408 structure, and wherein the composite material layer 406 is directly soft soldered to the metal reflective layer 403 at about 300 ° C with Au or Au-Sn, Alternatively, the composite material layer 406 and the metal reflective layer 403 may be directly bonded at a high temperature as required by the process. The layer structures (such as the substrate, the semiconductor layer, the metal reflective layer, the composite material layer, and the first electrode layer and the second electrode layer) according to the present embodiment are as defined in Embodiment 1.

According to the foregoing embodiment, and referring to FIG. 5A to FIG. 7, the light-emitting diode structure of the prior art may form a reflective metal layer (such as silver) on the semiconductor layer before the step of performing laser stripping, and then Connect a conductive support. However, the metal reflective layer tends to generate stress because the coefficient of thermal expansion is much larger than that of the semiconductor layer (such as GaN). In view of this, the current of the conventional light-emitting diode is infiltrated along the minimum resistance when the current is energized, and the local temperature of the stress is rapidly increased, and the metal reflective layer will support the lattice of the semiconductor layer. And because of the frequent switching of the LED, the crystal lattice of the semiconductor layer is repeatedly pulled to continuously produce defects, and it is easy to cause peeling between the metal reflective layer and the semiconductor layer (as shown in FIGS. 5A and 5B), resulting in a light-emitting diode. The brightness will be reduced quickly. At this time, if the carbon layer of the borrowed diamond is used in the present invention to have a high thermal conductivity, the waste heat generated when the light emitting diode emits light is quickly eliminated, and the semiconductor layer can be obtained by greatly reducing the effect of the interface stress. There will be no problems such as light decay or service life caused by internal lattice defects due to uneven current density distribution (Figure 6).

Furthermore, the composite material layer and the diamond-like carbon layer included in the present invention are exemplified by the light-emitting diode structure including the drill-copper composite layer, and the analysis thereof is as shown in FIG. 7, and it can be clearly seen according to the present invention. Effective control of the coefficient of thermal expansion also reduces thermal resistance.

The coefficient of thermal expansion (CTE) of the composite layer in the above embodiments of the present invention can be adjusted according to the particle size and volume percentage of the diamond, as described above, in order to control the preferred CTE value (eg, at 2-10 ppm/°C). Between), so the preferred diamond volume fraction is 30-50 Vol% (as shown in Figure 8), and the preferred diamond particle size is shown in Figure 9; more optional carbide can be used as needed The weight percentage of the agent is 2-5 wt%, and the carbide aid may be Fe, Co, Ni, Cr, Ti, or B, or the like.

Therefore, according to the light-emitting diode obtained by the manufacturing method of the embodiment, a vertical light-emitting type having a large size (>1 mm), a large current (>1 A/mm ² ), and a high power (>10 W) can be realized. In the polar body, it is better than paralleling a plurality of conventional light-emitting diodes that use current to bend current. Therefore, it has better luminous efficiency to make it brighter, and the excellent thermal conductivity of the carbon layer is used to eliminate the waste heat generated when the light is emitted, and to solve the internal defects to make it more durable.

The above-mentioned embodiments are merely examples for convenience of description, and the scope of the claims is intended to be limited to the above embodiments.

100‧‧‧Lighting diode

101‧‧‧Substrate

102, 302, 402‧‧‧ semiconductor layer

107‧‧‧ positive electrode

108‧‧‧Negative electrode

201‧‧‧Substrate

202‧‧‧Semiconductor layer

203, 303, 403‧‧‧ metal reflective layer

204, 304‧‧‧ middle layer

205, 305‧‧‧Drilling carbon layer

206, 306‧‧‧ Composite layers

207, 307, 407‧‧‧ first electrode

208, 308, 408‧‧‧ second electrode

FIG. 1 is a schematic view showing the structure of a light-emitting diode in the prior art.

2A to 2E are schematic flow charts showing a method of manufacturing a vertical light-emitting diode according to a preferred embodiment of the present invention.

3 is a schematic structural view of a straight light emitting diode according to another preferred embodiment of the present invention.

4 is a schematic structural view of a straight light emitting diode according to still another preferred embodiment of the present invention.

5A to 5B are diagrams showing the electron micrograph of the peeling of the electroplated metal and the semiconductor layer interface in the conventional light-emitting diode structure, if only mechanically and without chemical bonding.

Fig. 6 is a partial electron micrograph of a portion of a straight light emitting diode according to a preferred embodiment of the present invention.

Figure 7 is a graph comparing the thermal diffusivity and heat transfer coefficient of a drill-copper composite layer in accordance with a preferred embodiment of the present invention.

8 to 9 are graphs showing a comparison of diamond volume fractions of composite layers in a preferred embodiment of the present invention.

202. . . Semiconductor layer

203. . . Metal reflective layer

204. . . middle layer

205. . . Diamond-like carbon layer

206. . . Composite layer

207. . . First electrode

208. . . Second electrode

Claims (74)

A method for manufacturing a vertical light-emitting diode, comprising the steps of: providing a substrate; forming a semiconductor layer on the substrate, the semiconductor layer having a compound composed of elements of Group II to VI; forming a a metal reflective layer bonded to the semiconductor layer; forming at least one intermediate layer and at least one type of drilled carbon layer; forming a composite material layer; removing the substrate; and forming a first electrode layer and a second electrode layer Provided on one side of the semiconductor layer and the composite material layer, wherein the at least one intermediate layer and the at least one type of drilled carbon layer are stacked on one side of the metal reflective layer in a stacked manner, and the The composite layer has a coefficient of thermal expansion of 2 to 10 ppm/°C. The manufacturing method according to claim 1, wherein the substrate is Al ₂ O ₃ (sapphire), Si, SiC, GaAs, GaP, AlP, GaN, C (graphite), hBN, or C ( a substrate of diamonds; or a substrate having at least one cation of a nitride, a phosphide, or an arsenide of B, Al, Ga, In, Be, Mg. The manufacturing method of claim 1, wherein the removing step of the substrate is separated from the semiconductor layer by a laser. The manufacturing method of claim 1, wherein the semiconductor layer, the metal reflective layer, the at least one intermediate layer, and the at least one type of drill The carbon layer is formed by deposition of cathodic arc, sputtering, evaporation, electroplating, electroless plating, or coating. The manufacturing method according to claim 1, wherein the semiconductor layer is composed of Al ₂ O ₃ (sapphire), Si, SiC, GaAs, GaP, AlP, GaN, C (graphite), hBN, or C (diamond); or at least one cation is a nitride, phosphide, or arsenide of B, Al, Ga, In, Be, Mg. The manufacturing method according to claim 1, wherein the metal reflective layer is at least one selected from the group consisting of Ag, Al, Ni, Co, Pd, Pt, Au, Zn, Sn, Sb, Pb, Cu, CuAg, NiAg, and a group of the aforementioned metal alloys. The manufacturing method according to claim 1, wherein the metal reflective layer has a thickness of 100 to 500 nm. The manufacturing method according to claim 1, wherein the intermediate layer comprises at least one selected from the group consisting of Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W, and an alloy of the foregoing metals. Group. The manufacturing method according to claim 1, wherein the intermediate layer has a thickness of 50 to 500 nm. The manufacturing method of claim 1, wherein the composite material layer comprises a composite material composed of at least one metal and diamond, and the diamond is in a single layer, a plurality of layers, or Randomly distributed cloth arrangement. The manufacturing method of claim 10, wherein the diamond is 25-60% of the total volume of the composite layer. The manufacturing method of claim 10, wherein the diamond is 30-50% of the total volume of the composite layer. The manufacturing method according to claim 10, wherein the metal is at least one selected from the group consisting of Cu, Ag, Co, Ni, W, Fe, Ti, Cr, and B. The manufacturing method according to claim 10, wherein the diamond is a synthetic diamond grits. The manufacturing method according to claim 10, wherein the diamond has a particle diameter of from 1 μm to 1 mm. The manufacturing method according to claim 1, wherein the composite material layer has a thickness of 100 to 500 μm. The manufacturing method of claim 1, further comprising the step of polishing the surface of the composite material layer to Ra < 1 μm. The manufacturing method of claim 1, further comprising a transparent diamond-like carbon layer formed on one side of the semiconductor layer. The manufacturing method according to claim 18, wherein the transparent diamond-like carbon layer is formed by plasma chemical vapor deposition (PECVD). The manufacturing method according to claim 18, wherein the transparent diamond-like carbon layer comprises a hydrogen atom therein. The manufacturing method according to claim 20, wherein the hydrogen atomic system accounts for 15 to 40 at% of the transparent diamond-like carbon layer. A method for manufacturing a vertical light-emitting diode, comprising the steps of: providing a substrate; forming a semiconductor layer on the substrate, the semiconductor layer having a compound composed of elements of Group II to VI; Forming a metal reflective layer to be bonded to the semiconductor layer; forming a composite material layer having a thermal expansion coefficient of 2 to 10 ppm/° C.; removing the substrate; and forming a first electrode layer and a The second electrode layer is disposed on one side of the semiconductor layer and the composite material layer, respectively. The manufacturing method according to claim 22, wherein the composite material layer is directly soft-bonded to the metal reflective layer by Au or Au-Sn at about 300 ° C, or directly combined by high temperature bonding. a material layer and the metal reflective layer. The manufacturing method according to claim 22, wherein the substrate is Al ₂ O ₃ (sapphire), Si, SiC, GaAs, GaP, AlP, GaN, C (graphite), hBN, or C ( a substrate of diamonds; or a substrate having at least one cation of a nitride, a phosphide, or an arsenide of B, Al, Ga, In, Be, Mg. The manufacturing method of claim 22, wherein the removing step of the substrate is separated from the semiconductor layer by a laser. The manufacturing method according to claim 22, wherein the semiconductor layer and the metal reflective layer are formed by deposition of cathodic arc, sputtering, vapor deposition, electroplating, electroless plating, or coating. The manufacturing method according to claim 22, wherein the semiconductor layer is composed of Al ₂ O ₃ (sapphire), Si, SiC, GaAs, GaP, AlP, GaN, C (graphite), hBN, or C (diamond); or at least one cation is a nitride, phosphide, or arsenide of B, Al, Ga, In, Be, Mg. The manufacturing method according to claim 22, wherein the metal reflective layer is at least one selected from the group consisting of Ag, Al, Ni, Co, Pd, Pt, Au, Zn, Sn, Sb, Pb, Cu, CuAg, NiAg, and a group of the aforementioned metal alloys. The manufacturing method according to claim 22, wherein the metal reflective layer has a thickness of 100 to 500 nm. The manufacturing method of claim 22, wherein the composite material layer comprises a composite material composed of at least one metal and diamond, and the diamond is in a single layer, a plurality of layers, or Randomly distributed cloth arrangement. The manufacturing method of claim 30, wherein the diamond is 25-60% of the total volume of the composite layer. The manufacturing method of claim 30, wherein the diamond is 30-50% of the total volume of the composite layer. The manufacturing method according to claim 30, wherein the metal is at least one selected from the group consisting of Cu, Ag, Co, Ni, W, Fe, Ti, Cr, and B. The manufacturing method according to claim 30, wherein the diamond is a synthetic diamond grits. The manufacturing method according to claim 30, wherein the diamond has a particle diameter of from 1 μm to 1 mm. The manufacturing method according to claim 22, wherein the composite material layer has a thickness of 100 to 500 μm. The manufacturing method according to claim 22, further comprising the step of polishing the surface of the composite material layer to Ra < 1 μm. The manufacturing method according to claim 22, further comprising a transparent diamond-like carbon layer formed on one side of the semiconductor layer. The manufacturing method according to claim 38, wherein the transparent diamond-like carbon layer is formed by plasma chemical vapor deposition (PECVD). The manufacturing method according to claim 39, wherein the transparent diamond-like carbon layer comprises a hydrogen atom therein. The manufacturing method according to claim 40, wherein the hydrogen atomic system accounts for 15 to 40 at% of the transparent diamond-like carbon layer. A vertical light emitting diode comprising: a semiconductor layer having a compound composed of elements of Group II to VI; a metal reflective layer bonded to the semiconductor layer; at least one intermediate layer; at least one type a carbon layer; a composite material layer; and a first electrode layer and a second electrode layer respectively disposed on the side of the semiconductor layer and the composite material layer; wherein the at least one intermediate layer and the at least one type of drill The carbon layers are stacked on one side of the metal reflective layer in a stacked manner, and the composite material layer has a thermal expansion coefficient of 2 to 10 ppm/° C. The vertical light-emitting diode according to claim 42, wherein the semiconductor layer is composed of Al ₂ O ₃ (sapphire), Si, SiC, GaAs, GaP, AlP, GaN, C (graphite). , hBN, or C (diamond); or at least one cation is a nitride, phosphide, or arsenide of B, Al, Ga, In, Be, Mg. The vertical light-emitting diode according to claim 42, wherein the metal reflective layer is at least one selected from the group consisting of Ag, Al, Ni, Co, Pd, Pt, Au, Zn, Sn, Sb, Pb, A group consisting of Cu, CuAg, NiAg, and the aforementioned metal alloy. The vertical light-emitting diode according to claim 42, wherein the metal reflective layer has a thickness of 100-500 nm. The vertical light-emitting diode according to claim 42, wherein the intermediate layer comprises at least one selected from the group consisting of Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W, and the foregoing metal. A group of alloys. The vertical light-emitting diode according to claim 42, wherein the intermediate layer has a thickness of 50-500 nm. The vertical light-emitting diode according to claim 42, wherein the composite material layer comprises a composite material composed of at least one metal and diamond, and the diamond has a single layer in the composite material layer. , multi-layer, or randomly distributed cloth arrangement. The vertical light-emitting diode according to claim 48, wherein the diamond accounts for 25-60% of the total volume of the composite layer. The vertical light-emitting diode according to claim 48, wherein the diamond is 30-50% of the total volume of the composite layer. The vertical light-emitting diode according to claim 48, wherein the metal is at least one selected from the group consisting of Cu, Ag, Co, Ni, W, Fe, Ti, Cr, and BCu, Ag, Co, Ni, A group consisting of W, Fe, Ti, and Cr. The vertical light-emitting diode according to claim 48, wherein the diamond is a synthetic diamond grits. The vertical light-emitting diode according to claim 48, wherein the diamond has a particle diameter of 1 μm to 1 mm. The vertical light-emitting diode according to claim 42, wherein the composite material layer has a thickness of 100-500 μm. The vertical light-emitting diode according to claim 42, wherein the surface of the composite material layer has a polishing to Ra<1 μm. The vertical light-emitting diode of claim 42, further comprising a transparent diamond-like carbon layer on one side of the semiconductor layer. The vertical light-emitting diode according to claim 56, wherein the transparent diamond-like carbon layer comprises a hydrogen atom therein. The vertical light-emitting diode according to claim 57, wherein the hydrogen atomic system accounts for 15 to 40 at% of the transparent diamond-like carbon layer. A vertical light emitting diode comprising: a semiconductor layer having a compound composed of elements of Group II to VI; a metal reflective layer bonded to the semiconductor layer; a composite material layer, the composite The material layer has a thermal expansion coefficient of 2 to 10 ppm/° C.; and a first electrode layer and a second electrode layer respectively disposed on one side of the semiconductor layer and the composite material layer. The vertical light-emitting diode according to claim 59, wherein the composite material layer is directly soft-welded to Au or Au at about 300 ° C. The metal reflective layer or the composite material layer and the metal reflective layer are bonded directly at a high temperature. The vertical light-emitting diode according to claim 59, wherein the semiconductor layer is composed of Al ₂ O ₃ (sapphire), Si, SiC, GaAs, GaP, AlP, GaN, C (graphite). , hBN, or C (diamond); or at least one cation is a nitride, phosphide, or arsenide of B, Al, Ga, In, Be, Mg. The vertical light-emitting diode according to claim 59, wherein the metal reflective layer is at least one selected from the group consisting of Ag, Al, Ni, Co, Pd, Pt, Au, Zn, Sn, Sb, Pb, A group consisting of Cu, CuAg, NiAg, and the aforementioned metal alloy. The vertical light-emitting diode according to claim 59, wherein the metal reflective layer has a thickness of 100-500 nm. The vertical light-emitting diode according to claim 59, wherein the composite material layer comprises a composite material composed of at least one metal and diamond, and the diamond has a single layer in the composite material layer. , multi-layer, or randomly distributed cloth arrangement. The vertical light-emitting diode according to claim 64, wherein the diamond is 25-60% of the total volume of the composite layer. The vertical light-emitting diode according to claim 64, wherein the diamond is 30-50% of the total volume of the composite layer. The vertical light-emitting diode according to claim 64, wherein the metal is at least one selected from the group consisting of Cu, Ag, Co, Ni, W, Fe, Ti, Cr, and BCu, Ag, Co, Ni, A group consisting of W, Fe, Ti, and Cr. The vertical light-emitting diode according to claim 64, wherein the diamond is a synthetic diamond grits. The vertical light-emitting diode according to claim 64, wherein the diamond has a particle diameter of 1 μm to 1 mm. The vertical light-emitting diode according to claim 59, wherein the composite material layer has a thickness of 100-500 μm. The vertical light-emitting diode according to claim 59, wherein the surface of the composite material layer has a polishing to Ra<1 μm. The vertical light-emitting diode according to claim 59, further comprising a transparent diamond-like carbon layer on one side of the semiconductor layer. The vertical light-emitting diode according to claim 72, wherein the transparent diamond-like carbon layer comprises a hydrogen atom therein. The vertical light-emitting diode according to claim 73, wherein the hydrogen atomic system accounts for 15 to 40 at% of the transparent diamond-like carbon layer.