TWI679774B - Patterned photovoltaic substrate with enhanced photoelectricity function, light emitting diode and manufacturing method thereof - Google Patents

Abstract

The invention provides a method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function, including: providing a substrate; etching the surface of the substrate to form a first patterned structure and a spaced region; and forming a two metal layer on the first patterned structure and a spaced region. The surface; forming a second patterned structure on one or both of the first patterned structure and above the spaced region; etching the second patterned structure to extend down to the surface of the substrate portion; so that the spaced region forms a flat surface; The metal layer is removed to form a substrate having a first patterned structure, a second patterned structure, and a flat spaced region. In addition, the present invention further provides a patterned photovoltaic substrate with enhanced photoelectricity function manufactured by the above method, and a light emitting diode having the substrate.

Description

Patterned photovoltaic substrate with enhanced photoelectricity function, light emitting diode and manufacturing method thereof

The invention relates to a patterned photovoltaic substrate with enhanced photoelectricity function and a manufacturing method thereof, in particular to a patterned photovoltaic substrate having a flat surface space region, and a light emitting diode having the substrate, so as to improve the differential discharge Defects and electrical problems further strengthen the electrical functions of the light emitting diode.

The historical development of human lighting has entered the era of solid-state lighting. Brighter brightness, lower prices, longer life, higher stability, etc. are the common goals pursued by the solid-state lighting industry. In the lighting market, the brightness requirements of light-emitting diodes are the first. In general, the maximum light output (L _max ) of a light-emitting diode is mainly determined by the external quantum efficiency (η _ext ) and the maximum operating current (I _max ), that is, L _max = η _ext × I _max , where the external quantum efficiency (η _ext ) is again determined by the internal quantum efficiency (η _int ) and the light extraction efficiency (η _extr ), that is, η _ext = η _int × η _extr . At present, the internal quantum efficiency of blue light-emitting diodes has generally reached more than 70%, but the internal quantum efficiency of green light-emitting diodes has suddenly dropped to less than 40%. Therefore, the internal quantum efficiency and light extraction efficiency have been improved to improve There is still much room for the external quantum efficiency of a light emitting diode or increasing the light emitting brightness of the light emitting diode.

Because the degree of lattice mismatch between GaN and sapphire substrate is as high as 16%, when using sapphire substrate as the substrate to perform epitaxial GaN thin film, there will be stress in the GaN thin film, and many different types will appear. Differential defect, which makes the differential discharge density of GaN film reach 10 ⁹ to 10 ¹⁰ cm ^-2 , which seriously affects the quality of the epitaxial film, and the defect usually acts as a non-radiative recombination center, resulting in a decrease in luminous efficiency. Therefore, the key to the development of patterned sapphire substrate manufacturing technology is to reduce the defect density in order to substantially improve the epitaxial quality of GaN thin films and increase the luminous brightness. By growing the GaN thin film on the sidewall of the pattern substrate to change the growth direction of the GaN thin film differential defect, the differential defect will be bent by 90 °, which will eliminate the defect by interlacing each other to form a stacking misalignment, and transmit three-dimensional stress during epitaxy. Releasing reduces the formation of defects and reduces the differential density within the film to improve crystal quality. Current research has also pointed out that the use of patterned sapphire substrates for the growth of GaN films has been found to reduce the density of differential defects to 10 ⁸ to 10 ⁹ cm ^-2 and further increase the internal quantum efficiency and luminous brightness of light-emitting diodes.

As mentioned above, in the structure with a pattern on the substrate, if the pattern on the substrate includes various patterns of microstructure or submicron structure, the area of the C-plane area without a pattern will be reduced, which will increase the epitaxial layer during the epitaxial process Difficulties in the medium cause the problem of poor row, and further affect the electrical function of the LED, such as weakening of antistatic ability. In addition, if this substrate is used as the LED substrate, the reverse leakage current of the LED will be increased, and the LED will also easily generate heat.

In the latest research, sub-micron-scale pattern substrates are also used to grow light-emitting diode structures. For pattern substrates of the same area, reducing the pattern size and increasing the number of patterns will increase the area of the effective area for lateral growth and enhance the lateral growth mechanism. As a result, it is easier to change the growth direction and form stacking misalignment to eliminate differential defects, and greatly reduce the internal differential density of the film. At the same time, due to the short pattern spacing, it is easy to form voids during the epitaxial growth of gallium nitride to prevent the extension of defects and improve the nitride. Epitaxial quality of gallium thin film. The research results show that the growth of gallium nitride films using micron-scale patterned sapphire substrates can reduce the differential density to 10 ⁸ cm ^-2 . If the pattern substrate is changed to sub-micron scale, the degree of stress release per unit volume can be increased. The differential row density is reduced to 10 ⁷ cm ^-2 or lower.

In the known technology, such as the Republic of China Publication Patent No. I396297, a light-emitting diode is disclosed, including: a substrate having micron-sized holes therein; and a nano-sized porous photonic crystal structure as a buffer layer formed on the substrate. The first type epitaxial layer is formed on the porous photonic crystal structure of the buffer layer; the light emitting layer is formed on the first type epitaxial layer; the second type epitaxial layer is formed on the light emitting layer; A first contact electrode is formed on the first type epitaxial layer; and a second contact electrode is formed on the second type epitaxial layer.

Another published patent of the Republic of China No. 201251113 discloses a method for manufacturing an LED substrate, an LED substrate, and a white LED structure. The main purpose is to make the LED emit high-brightness white light with good color rendering. The reflective surface of the substrate forms a plurality of numbers. The convex particles with curved surfaces on the top, the width of the bottom of these convex particles is 2 micrometers to 4 micrometers, the height of 1.2 micrometers to 1.8 micrometers, and the distance between adjacent convex particles is 0.6 micrometers to 3 micrometers. The indium gallium epitaxial layer emits ultraviolet light with a wavelength in the range of 380 to 410 nanometers after being energized. The ultraviolet light is reflected by the reflective surface of the substrate and the raised particles, and excites the mixed zinc oxide and yttrium aluminum garnet. Fluorescent substances generate complementary color light of ultraviolet light, and after mixing with each other, a package body scatters high-brightness white light with good color rendering, which can be used for lighting and other purposes.

However, in the above-mentioned inventive diodes, a nanometer-sized porous photonic crystal structure or micron-sized convex particles are mainly formed on the substrate to improve the luminous efficiency of the light-emitting diode. However, the micron-sized or Nano-level structural design still has its inherent limitations in reducing the degree of differential row density or strengthening the photoelectricity function.

In addition, as in the Republic of China Patent Application No. 102111662 filed by the applicant of the present application, a substrate for a photovoltaic element is disclosed, and at least one photovoltaic element is provided on an upper surface of the substrate, characterized in that the upper surface of the substrate has The plurality of micro-structures and the plurality of sub-micro-structures constitute a rough surface, wherein the sizes of the sub-micro structures are smaller than the micro-structures. In this way, the optical diffusion rate of the substrate can be improved, and the quality of the epitaxial thin film material grown on the substrate can be improved, thereby improving the light extraction efficiency of the photovoltaic element and achieving the luminous brightness of the entire photovoltaic element. The invention further provides a photovoltaic element. Among them, the previous case is a combination of micro-structure and sub-micro-structure proposed by the applicant of the present application to improve the quality of the epitaxial thin film material or the luminous brightness of the overall photovoltaic device.

Therefore, there is an urgent need to develop a patterned photovoltaic substrate with enhanced photoelectricity function and a light emitting diode having the substrate, which can effectively reduce the differential defect density of the gallium nitride film and increase the light emitting efficiency of the light emitting diode. In order to further improve the applicability and value of light-emitting diodes, there is a need for them.

The main purpose of the present invention is to provide a method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function. The steps include:

Step S1: providing a substrate;

Step S2: forming a first patterned structure and a space region on the surface of the substrate by a first etching process;

Step S3: forming a first metal layer and a second metal layer on the first patterned structure and the surface of the space region on the substrate;

Step S4: forming a second patterned structure on the second metal layer by a second etching process, the second patterned structure is located on one of the first patterned structure and above the gap region or Both

Step S5: the third patterned structure is extended downward to the first metal layer and a part of the surface of the substrate by a third etching process;

Step S6: performing a fourth etching process for a predetermined time so that the interval region is a flat surface; and

Step S7: removing the second metal layer and the first metal layer from the substrate by an acid solution to form the first patterned structure as a micron-scale protruding structure, and the second patterned structure as The primary micron-scale groove structure and the substrate with the spaced region as a flat surface.

The method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function according to the present invention, wherein step S6 further includes a preset condition, including: an etching gas flow rate between 1 and 40 standard cubic centimeters per minute; A substrate bias voltage is between 50 and 700 watts; and a power supply is between 150 and 1200 watts.

The method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function provided by the present invention, wherein the predetermined time is between 150 seconds and 1000 seconds.

The method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function provided by the present invention further includes a step S8: providing a two-dimensional material layer formed on the spaced region and above the first patterned structure.

The manufacturing method of the patterned photovoltaic substrate with enhanced photoelectricity function provided by the present invention, wherein the two-dimensional material layer includes graphene.

According to the present invention, a method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function, wherein the graphene is generated by the following steps: a copper layer is disposed on the space region; and hydrogen, methane, and the copper layer are used to produce the graphene. A chemical action causes a graphene layer to be generated above the copper layer and below the copper layer; removing the graphene layer above the copper layer; and removing the copper layer so as to leave the copper layer The graphene layer is on the spaced region.

In the method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function, the copper layer is produced by a thermal evaporation method or a sputtering method.

In the method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function, the thickness of one of the copper layers is between 50 and 500 nanometers.

The method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function according to the present invention, wherein the chemical action of the hydrogen, the methane, and the copper layer generates the graphene layer at an operating temperature of 300 to 1500 degrees.

The invention further provides a patterned photovoltaic substrate with enhanced photoelectricity function, including:

A first patterned structure, which is a micron-scale protruding structure;

A spaced area that is a flat surface; and

A second patterned structure is a micron-level groove structure and is formed on the first patterned structure.

The patterned photovoltaic substrate with enhanced photoelectricity function provided by the present invention further includes a two-dimensional material layer formed on the interval region and above the first patterned structure.

The patterned photovoltaic substrate with enhanced photoelectricity function provided by the present invention, wherein the two-dimensional material layer includes graphene.

The present invention further provides a light-emitting diode of a patterned photovoltaic substrate with enhanced photoelectricity function, including:

A substrate, which is a patterned photovoltaic substrate with enhanced photoelectricity function according to any one of the foregoing;

A buffer layer disposed on the substrate; and

A photovoltaic element is disposed on the buffer layer and includes a first semiconductor layer, a light emitting layer, and a second semiconductor layer;

The first semiconductor layer is bonded to the buffer layer, and the light emitting layer is sandwiched between the first semiconductor layer and the second semiconductor layer.

The light-emitting diode of the patterned photovoltaic substrate with enhanced photoelectricity function provided by the present invention further includes a two-dimensional material layer formed on the spaced region of the substrate and above the first patterned structure.

The light-emitting diode of the patterned photovoltaic substrate with enhanced photoelectricity function provided by the present invention, wherein the two-dimensional material layer includes graphene.

The light-emitting diode of the patterned photovoltaic substrate with enhanced photoelectricity function provided by the present invention, wherein the buffer layer is aluminum nitride (Aluminum Nitride).

The light-emitting diode of the patterned photovoltaic substrate with enhanced photoelectricity function provided by the present invention, wherein the buffer layer is disposed on the two-dimensional material layer of the substrate.

The following is a description of specific embodiments of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied by other different specific embodiments, and various details in this specification can also be modified and changed for different viewpoints and applications without departing from the spirit of the present invention.

Please refer to FIG. 1, which is a flowchart of steps of a method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function according to the present invention. The steps include:

Step S1: Provide a substrate 10; please refer to FIG. 2A. In one embodiment, the substrate 10 is a sapphire substrate with a flat surface or a silicon substrate with a flat surface.

Step S2: Referring to FIG. 2B, a first patterned structure 11 and a space region 12 are formed on the surface of the substrate 10 by a first etching process. In one embodiment, the first etching process may be an isotropic etching or an anisotropic etching, and may be an inductively coupled plasma reactive ion etching (ICP) method. -RIE), chemical liquid etching, dry etching, plasma etching, or laser processing. In addition, isotropic etching can use a chemical etching solution (such as a strong acid) to perform a chemical etching reaction under a high temperature environment to produce a micron-level protrusion or groove structure with a certain periodicity on the substrate 10; in addition, anisotropic The etching procedure is to first form a patterned photoresist layer on the substrate 10, and then use inductively coupled plasma reactive ion etching (ICP-RIE) technology to perform etching to selectively remove part of the substrate 10, which can also achieve the above. The purpose of forming a micron-scale protrusion or groove structure with a certain periodicity.

In addition, in step S2, it further includes providing a first photoresist layer (not shown) disposed on a part of the surface of the substrate 10, so that the first etching process can selectively remove part of the substrate 10; In the aforementioned method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function of the present invention, the first patterned structure 11 may be a micron-level protruding structure (as shown in FIG. 2B) or a micron-level groove structure, and The separation region 12 may be a planar structure. In one embodiment of the present invention, the first patterned structure 11 may be a one-micron-scale protruding structure having a height of 1.2 micrometers to 2 micrometers and an outer diameter of 1 micrometer to 5 micrometers. The distance between the structures 11 (that is, the length or width of the spacing region 12) is 0.3 μm to 1 μm. In addition, in another embodiment of the present invention, the first patterned structure 11 may be a micron-level groove structure, which will be described in detail later.

Step S3: Please refer to FIG. 2C, forming the first patterned structure 11 and the space 12 of the first metal layer 13 and the second metal layer 14 on the substrate 10. The first metal layer 13 or the second metal layer 14 can be formed by a coating method, a chemical plating method, a sputtering method, a vapor deposition method, a cathodic arc method, or a chemical vapor deposition method. Among them, the vapor deposition method The method includes an electron beam evaporation method, a thermal evaporation method, a high frequency evaporation method, or a laser evaporation method, and the present invention is not limited thereto. Here, in a method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function disclosed in the present invention, the first metal layer 13 is at least one selected from the group consisting of titanium, chromium, molybdenum, or silicon dioxide (SiO ₂ ). The group is formed, and the thickness of the first metal layer 13 may be 1 nanometer to 1 micrometer. In addition, the second metal layer 14 is aluminum, and the thickness of the second metal layer 14 may be 10 nanometers to 100 micrometers. In another embodiment of the present invention, the first metal layer 13 is mainly titanium.

Step S4: Referring to FIG. 2D, a second patterned structure 15 is formed on the second metal layer 14 by a second etching process. The second patterned structure 15 is located on the first patterned structure 11 and above the spacer region 12. Either or both. In one embodiment, the second etching process is an anodic aluminum oxide (AAO) process, but it is not limited thereto. In the case of using anodized aluminum, it includes providing a second photoresist layer on the surface of the second metal layer 14 above the first patterned structure 11, so that the anodized aluminum can be selectively removed. The second metal layer 14 above the spacer region 12, therefore, the second patterned structure 15 may be formed on the second metal layer 14 above the spacer region 12, but the second metal layer 14 above the first patterned structure 11 is It will not have the second patterned structure 15. In another embodiment, in the aforementioned method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function of the present invention, in step S4, it further includes providing a second photoresist layer disposed on the second region over the second metal 12 On the surface of the layer 14, the anodized aluminum treatment can selectively remove a portion of the second metal layer 14 above the first patterned structure 11. Therefore, the second patterned structure 15 can be formed above the first patterned structure 11. The second metal layer 14, but the second metal layer 14 above the spacer region 12 does not have the second patterned structure 15.

Step S5: Please refer to FIG. 2E. The third patterning structure 15 is extended downward to the first metal layer 13 and a part of the surface of the substrate 10 through a third etching process. The third etching process described herein can be performed in the same manner. The foregoing first etching process is not repeated here.

Step S6: Referring to FIG. 2F and FIG. 2G, a fourth etching process is performed for a predetermined time, so that the interval region 12 becomes a flat surface. In this step, the predetermined time may be between 150 seconds and 1000 seconds. At the beginning of a predetermined time, the surface of the substrate 10 changes as shown in FIG. 2F. The fourth etching process performed on the space region 12 The etching rate will be higher than that of the first patterned structure 11. When the predetermined time continues, the surface of the substrate 10 changes as shown in FIG. 2G. The first metal layer 13 and the second metal layer on the upper surface of the spacer region 12 14 has been removed, and the spacer region 12 has become a planarized structure, while the top of the first patterned structure 11 remains. It should be particularly noted that in order to achieve a flat surface optimized for the surface of the spacer region 12, the fourth etching process further includes a preset condition, including: an etching gas flow rate, between 1 and 40 standard cubic centimeters per minute. (sccm, standard cubic centimeter per minute); a substrate bias voltage between 50 and 700 watts; a working chamber pressure between 1 and 25 millimeter torr; and a power supply, Between 150 and 1200 watts. In one embodiment of the present invention, the etching gas includes boron trichloride.

Step S7: Referring to FIG. 2H, an acid solution is used to remove the remaining second metal layer 14 and the first metal layer 13 from the substrate 10 to form the first patterned structure 11 as a micron-scale protruding structure, The second patterned structure 15 is a primary micro-scale groove structure, and the substrate 10 with a flat surface in the spacing region 12.

Wherein, the second patterned structure 15 is a pyramid-shaped sub-micron groove structure, with a depth of 10 nanometers to 10 micrometers and an outer diameter of 20 nanometers to 950 nanometers, so that the first patterned structure 11 contains a second The number of the patterned structures 15 is 1 × 10 ⁸ to 2.5 × 10 ¹¹ per cm 2.

As mentioned above, the core focus of the present invention is to planarize the surface of the spacer region 12 to improve the problem of poor epitaxial yield over the spacer region 12. The method for planarizing includes etching, which is not limited in the present invention. The predetermined time refers to a time for flattening the surface of the interval region 12 and is between 150 seconds and 1000 seconds, which is determined according to the substrate material and the aspect ratio of the groove structure. The deeper the groove structure, the longer it takes to flatten; the shallower the groove structure, the shorter the time it takes to planarize.

Please refer to FIG. 3A to FIG. 6D, which are scanning electron microscope image images generated by the method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function according to the present invention according to at least one of the preset conditions. In this embodiment, this preset condition is as follows, but not limited to this: the vacuum pressure is 5 * 10 ^-3 torr, the boron chloride is released 30 sccm, the power is 400 watts, and the bias power is 300 watt Scanning electron microscope images after etching for 250 seconds, 300 seconds, 350 seconds, and 400 seconds, respectively, are FIG. 3A to FIG. 3D, FIG. 4A to FIG. 4D, FIG. 5A to FIG. 5D, and FIG. 6A to FIG. 6D. Each figure has a top view of 6000 times, 10,000 times, and 20,000 times, and a cross-sectional view of 20,000 times. The figure includes a first patterned structure 11, a space region 12, and a second patterned structure 15. It can be seen from FIG. 3A to FIG. 3D, FIG. 4A to FIG. 4D, FIG. 5A to FIG. 5D, and FIG. 6A to FIG. 6D that if the user fails to set the above-mentioned at least one preset condition and predetermined time of the present invention, Next, the completed substrate structure still has a part of the groove structure on the interval region. According to the method of the present invention, the at least one preset condition and the predetermined time are set, and the surface of the spaced region of the completed substrate structure is a flat surface, as shown in FIGS. 6A to 6D.

In addition, the method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function provided by the present invention further includes a step 8. Please refer to FIG. 2I, which includes providing a two-dimensional material layer 16 formed on the spacer region 12 and the first Above a patterned structure 11. In one embodiment of the present invention, the two-dimensional material layer 16 includes graphene, which has characteristics such as high electron mobility, high thermal conductivity, high current density, high mechanical strength, high flexibility, and light transparency. Accordingly, the present invention can further improve and improve the electrical function of the light emitting diode used as the substrate by adding the two-dimensional material layer 16 after planarizing the gap region 12.

As mentioned above, graphene is produced by the following steps: a copper layer is disposed on the space region. Through the chemical action of hydrogen, methane and the copper layer, a graphene layer is generated above the copper layer and below the copper layer, respectively. Remove the graphene layer over the copper layer. The copper layer is removed so as to leave the graphene layer under the copper layer on the spacer region.

In addition, in one embodiment of the present invention, the copper layer is generated by a thermal evaporation method or a sputtering method. The thickness of the copper layer is between 50 and 500 nanometers. The chemical action of the hydrogen, methane, and copper layers produces a graphene layer at an operating temperature of 300 to 1500 degrees. The method for removing the graphene layer on the copper layer and the method for removing the copper layer includes grinding and hydrochloric acid etching, which is not limited in the present invention.

In addition, the following describes various embodiments according to the method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function of the present invention, but the present invention is not limited thereto.

Please refer to FIG. 7A to FIG. 7C, which are schematic diagrams of a patterned photovoltaic substrate with enhanced photoelectricity function according to Embodiment 2 of the present invention. The embodiment 2 is substantially the same as the patterned photovoltaic substrate with enhanced photoelectricity function described in the foregoing embodiment 1 and the manufacturing process thereof, except that the uneven pattern of the first patterned structure is different. Different from the foregoing embodiment 1, the first patterned structure 11 (see FIG. 2B together) having a conical micro-scale protruding structure is provided. In the embodiment 2, a first photoresist layer is provided (not shown in the figure). ) Is disposed on a part of the surface of the substrate 20 so that the first etching process is to selectively remove a part of the substrate 20 to form a first patterned structure 21 having a conical micro-scale groove structure and a space region 22 of a planar structure Then, according to the manufacturing process of Embodiment 1, the first patterned structure 21 includes a plurality of second patterned structures 25 to form a patterned photovoltaic having the first patterned structure 21 and the second patterned structure 25. Substrate 20. In the diagram of FIG. 7B, the fourth etching process is performed on the interval region 22 for a predetermined time, so that the interval region 22 forms a flat surface. In the diagram of FIG. 7C, a two-dimensional material 26 is disposed above the spacer region 22 and the first patterned structure 21.

Please refer to FIG. 8A to FIG. 8I, which are schematic diagrams of patterned photovoltaic substrates with enhanced photoelectricity function in Embodiments 3 to 5 of the present invention. Embodiments 3 to 5 are substantially the same as the patterned photovoltaic substrates with enhanced photoelectricity function described in the foregoing embodiment 1 and the manufacturing process thereof, except that the shape of the first patterned structure is different.

Different from the first patterned structure 11 having a conical micron-scale protruding structure in Embodiment 1 (please refer to FIG. 2B together), please refer to FIGS. 8A to 8C. In Embodiment 3, a first photoresist is provided. A layer (not shown) is provided on a part of the surface of the substrate 301, so that the first etching process is to selectively remove a part of the substrate 301 to form a first patterned structure 311 and a plane having a triangular pyramid-shaped micron-scale protruding structure. The spacing region 321 of the structure; then, according to the manufacturing process of Embodiment 1, the first patterned structure 311 includes a plurality of second patterned structures 351 to form the first patterned structure 311 and the second patterned structure. Patterned photovoltaic substrate 301 of 351. In the diagram of FIG. 8B, the fourth etching process is performed on the interval region 321 for a predetermined time, so that the interval region 321 forms a flat surface. As shown in FIG. 8C, a two-dimensional material 36 is disposed above the spaced region 321 and the first patterned structure 351.

Please refer to FIGS. 8D to 8F. In Embodiment 4, a first photoresist layer (not shown) is provided on a portion of the surface of the substrate 302, so that the first etching process is to selectively remove a portion of the substrate 302. A first patterned structure 312 having a quadrangular pillar-shaped micrometer-scale protruding structure and a space region 322 of a planar structure are formed; then, according to the manufacturing process of Embodiment 1, the first patterned structure 312 contains a plurality of second The patterned structure 352 is formed to form a patterned photovoltaic substrate 302 having a first patterned structure 312 and a second patterned structure 352. In the diagram of FIG. 8E, the fourth etching process is performed on the interval region 322 for a predetermined time, so that the interval region 322 forms a flat surface. In the diagram of FIG. 8F, a two-dimensional material 37 is disposed on the spacer region 322 and the second patterned structure 352.

Please refer to FIGS. 8G to 8I. In Embodiment 5, a first photoresist layer (not shown) is provided on a part of the surface of the substrate 303, so that the first etching process is to selectively remove a part of the substrate 303. To form a first patterned structure 313 with a micrometer-scale protruding structure having a pentagonal columnar shape (ie, a combination of a triangular pyramid shape and a quadrangular columnar shape) and a space region 323 of a planar structure; The first patterned structure 313 includes a plurality of second patterned structures 353 to form a patterned photovoltaic substrate 303 having the first patterned structure 313 and the second patterned structure 353. In the diagram of FIG. 8H, the fourth etching process is performed on the interval region 323 for a predetermined time, so that the interval region 323 forms a flat surface. In the diagram of FIG. 8I, a two-dimensional material 38 is disposed on the spacer region 323 and the first patterned structure 313.

Please refer to FIGS. 9A to 9C, which are schematic diagrams of a patterned photovoltaic substrate with enhanced photoelectricity function according to Embodiment 6 of the present invention. Embodiment 6 is substantially the same as the patterned photovoltaic substrate with enhanced photoelectricity function described in the foregoing embodiment 1 and the manufacturing process thereof, except that the distribution position of the patterned photovoltaic substrate is different in the second patterned structure.

The second patterned structure different from Embodiment 1 is located above both the first patterned structure and the space region. Please refer to FIG. 9A. In Embodiment 6, a second photoresist layer is provided (not shown) The surface of the second metal layer (not shown in the figure) disposed on the first patterned structure 411, so that the anodized aluminum is treated to selectively remove a portion of the second metal layer above the spaced region 421; then, according to the embodiment The manufacturing process of 1 forms a patterned photovoltaic substrate 401 having a first patterned structure 411 and a second patterned structure 451. Among them, the first patterned structure 411 does not have the second patterned structure 451, but only in the space region 421 There is a second patterned structure 451 above. In the diagram of FIG. 9B, the fourth etching process is performed on the interval region 421 for a predetermined time, so that the interval region 421 forms a flat surface. In the diagram of FIG. 9C, a two-dimensional material 46 is disposed on the spacer region 421 and the first patterned structure 411.

Please refer to FIG. 10, which is a schematic diagram of a light-emitting diode of the patterned photovoltaic substrate with enhanced photoelectricity function in Embodiment 7 of the present invention. It provides a buffer layer and a photovoltaic element formed in the foregoing Embodiment 1 and has enhanced photoelectricity. Functionally pattern the photovoltaic substrate to form a light emitting diode.

The present invention further proposes a light-emitting diode of a patterned photovoltaic substrate with enhanced photoelectricity function. Please refer to FIG. 10. In this seventh embodiment, it includes: a substrate 10 whose structural characteristics are as described above. Any of the patterned photovoltaic substrates with enhanced photoelectricity function of any of Embodiments 1 to 6; a buffer layer 50 disposed on the substrate 10, which may be a gallium nitride layer, because the spacer region 12 of the substrate 10 It has a flat surface, and a two-dimensional material layer 56 is further arranged above. Here, the two-dimensional material layer 56 includes, but is not limited to, graphene. According to this, when the buffer layer 50 is disposed on the substrate 10, it is disposed in the middle. The two-dimensional material layer 56 can improve the problem of misalignment caused by the problem of lattice mismatch; and a photovoltaic element, the photovoltaic element is disposed on the buffer layer 50, and the photovoltaic element includes a first semiconductor layer 51 and a light emitting element. The layer 52 and the second semiconductor layer 53, wherein the first semiconductor layer 51 is bonded to the buffer layer 50, and the light emitting layer 52 is sandwiched between the first semiconductor layer 51 and the second semiconductor layer 53.

The above-mentioned substrate 10 has a first patterned structure 11, a spacer region 12, and a second patterned structure 15. The second patterned structure 15 is simultaneously formed on both the first patterned structure 11 and the spaced region 12. The pattern structure 11 is a micro-scale protruding structure, and the second patterned structure 15 is a sub-micron-scale groove structure. In addition, it includes a first electrode 54 and a second electrode 55, and the first electrode 54 and the second electrode 55 are respectively The first semiconductor 51 and the second semiconductor layer 53 are electrically bonded. In addition, it should be particularly noted that the space 12 of the substrate 10 has a flat surface by using the aforementioned manufacturing method.

Furthermore, it should be particularly noted that the patterned photovoltaic substrate with enhanced photoelectricity function provided by the present invention further includes a two-dimensional material layer 56 formed on the space region 12 and the first patterned structure 11. The two-dimensional material layer 56 includes, but is not limited to, graphene. According to this, a two-dimensional material layer is disposed on the surface of the substrate on the flat spaced region 12 and above the first patterned structure 11. Of course, the entire substrate For example, on the non-planar C-plane, the material of the two-dimensional material layer 56 may be long, such as graphene. In addition, the buffer layer 50 may be aluminum nitride, and the material of the substrate 10 may be sapphire. According to this, the two-dimensional material layer can improve the epitaxial quality or reduce the differential defect density of the gallium nitride film and reduce the reverse Leakage current, improve thermal conductivity, more excellent electrical function and antistatic ability.

The above embodiments are merely examples for the convenience of description. The scope of the claimed rights of the present invention should be based on the scope of the patent application, rather than being limited to the above embodiments.

S1, S2, S3, S4, S5, S6, S7, S8‧‧‧ steps
10, 20, 301, 302, 303, 401, 402‧‧‧ substrate
11, 21, 311, 312, 313, 411‧‧‧ the first patterned structure
12, 22, 321, 322, 323, 421‧‧‧ spaced areas
13‧‧‧ first metal layer
14‧‧‧Second metal layer
15, 25, 351, 352, 353, 451‧‧‧ second patterned structure
16, 26, 36, 37, 38, 46, 56‧‧‧ two-dimensional material layers
50‧‧‧ buffer layer
51‧‧‧First semiconductor layer
52‧‧‧Light-emitting layer
53‧‧‧Second semiconductor layer
54‧‧‧first electrode
55‧‧‧Second electrode

FIG. 1 is a flowchart of the steps of a method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function according to the present invention.
2A to 2I are schematic diagrams of a manufacturing process of a patterned photovoltaic substrate with enhanced photoelectricity function according to Embodiment 1 of the present invention;
3A to 6D are scanning electron microscope image diagrams generated according to at least one preset condition by the method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function according to the present invention;
7A to 7C are schematic diagrams of a patterned photovoltaic substrate with enhanced photoelectricity function according to Embodiment 2 of the present invention;
FIG. 8A to FIG. 8I are schematic diagrams of patterned photovoltaic substrates with enhanced photoelectricity function in Embodiments 3 to 5 of the present invention;
9A to 9C are schematic diagrams of a patterned photovoltaic substrate with enhanced photoelectricity function according to Embodiment 6 of the present invention;
FIG. 10 is a schematic diagram of a light-emitting diode having the patterned photovoltaic substrate with enhanced photoelectricity function according to Embodiment 7 of the present invention.

Claims (16)

A method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity functions, the steps include: step S1: providing a substrate; step S2: forming a first patterned structure and a space on the surface of the substrate by a first etching process Region; step S3: forming a first metal layer and a second metal layer on the substrate, the first patterned structure and the surface of the space region; step S4: processing the second metal layer by a second etching process A second patterned structure is formed thereon, the second patterned structure is located on one or both of the first patterned structure and above the space region; step S5: the third patterned structure is processed by a third etching process. Two patterned structures extend downward to the first metal layer and a part of the surface of the substrate; step S6: performing a fourth etching process for a predetermined time so that the space region is a flat surface; and step S7: using a Acid treatment to remove the second metal layer and the first metal layer from the substrate to form the first patterned structure as a micron-scale protruding structure, and the second patterned structure as a micron-level concave Structure, the spacer region and a flat surface of a substrate. According to the method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function described in item 1 of the scope of patent application, the step S6 further includes a preset condition, including: an etching gas flow rate, between 1 and 40 standard cubic meters per minute Centimeters; a substrate bias between 50 and 700 watts; and a power supply between 150 and 1200 watts. The method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function as described in item 2 of the scope of patent application, wherein the predetermined time is between 150 seconds and 1000 seconds. The method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function as described in item 1 of the scope of the patent application, further comprising a step S8: providing a two-dimensional material layer formed in the space region and the first patterned structure Up. The method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function as described in item 4 of the scope of the patent application, wherein the two-dimensional material layer includes graphene. As described in item 5 of the scope of the patent application, a method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function, wherein the graphene is generated by the following steps: a copper layer is disposed on the space region; and hydrogen, methane, and The chemical action of the copper layer causes a graphene layer to be generated above the copper layer and below the copper layer; removing the graphene layer above the copper layer; and removing the copper layer so as to leave The graphene layer under the copper layer is on the spacer region. The method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function as described in item 6 of the scope of the patent application, wherein the copper layer is produced by a thermal evaporation or sputtering method. According to the method for manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function described in item 6 of the scope of the patent application, one of the copper layers has a thickness between 50 and 500 nanometers. According to the method of manufacturing a patterned photovoltaic substrate with enhanced photoelectricity function described in item 6 of the scope of the patent application, wherein the chemical action of the hydrogen, the methane, and the copper layer is generated at an operating temperature of 300 to 1500 degrees. Graphene layer. A patterned photovoltaic substrate with enhanced photoelectricity function includes: a first patterned structure, which is a micron-level protruding structure; a spaced region, which has a flat surface; a second patterned structure, which is a one-micron level A groove structure is formed on the first patterned structure; and a two-dimensional material layer is formed on the spaced region having a flat surface and above the first patterned structure. The patterned photovoltaic substrate with enhanced photoelectricity function described in item 10 of the scope of the patent application, wherein the two-dimensional material layer includes graphene. A light-emitting diode of a patterned photovoltaic substrate having a function of enhancing photoelectricity, comprising: a substrate, the substrate being a patterned photovoltaic substrate having a function of strengthening photoelectricity according to any one of claims 10 to 11 of the scope of patent application A buffer layer disposed on the substrate; and a photovoltaic element disposed on the buffer layer and including a first semiconductor layer, a light emitting layer, and a second semiconductor layer; wherein the first semiconductor layer is Bonded to the buffer layer, the light emitting layer is sandwiched between the first semiconductor layer and the second semiconductor layer. As described in item 12 of the scope of the patent application, the light-emitting diode of the patterned photovoltaic substrate with enhanced photoelectricity function further includes a two-dimensional material layer formed on the spaced region of the substrate and above the first patterned structure. . As described in item 13 of the scope of the patent application, the light-emitting diode of the patterned photovoltaic substrate with enhanced photoelectricity function, wherein the two-dimensional material layer includes graphene. As described in item 12 of the scope of the patent application, the light-emitting diode of the patterned photovoltaic substrate with enhanced photoelectricity function, wherein the buffer layer is aluminum nitride (Aluminum Nitride). As described in item 15 of the scope of the patent application, the light-emitting diode of the patterned photovoltaic substrate with enhanced photoelectricity function, wherein the buffer layer is disposed on the two-dimensional material layer of the substrate.