WO2022077254A1 - 微型led结构的制作方法 - Google Patents

微型led结构的制作方法 Download PDF

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Publication number
WO2022077254A1
WO2022077254A1 PCT/CN2020/120822 CN2020120822W WO2022077254A1 WO 2022077254 A1 WO2022077254 A1 WO 2022077254A1 CN 2020120822 W CN2020120822 W CN 2020120822W WO 2022077254 A1 WO2022077254 A1 WO 2022077254A1
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Prior art keywords
substrate
led structure
micro led
opening
manufacturing
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PCT/CN2020/120822
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English (en)
French (fr)
Inventor
刘慰华
程凯
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苏州晶湛半导体有限公司
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Priority to PCT/CN2020/120822 priority Critical patent/WO2022077254A1/zh
Priority to CN202080105786.7A priority patent/CN116325183A/zh
Publication of WO2022077254A1 publication Critical patent/WO2022077254A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof

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  • the present application relates to the field of semiconductor technology, and in particular, to a method for fabricating a micro LED structure.
  • ⁇ LED miniature LED, size less than 50 ⁇ m
  • the size of the ⁇ LED single chip belongs to the micron level.
  • the typical ⁇ LED single chip size is 5 ⁇ m*5 ⁇ m.
  • the current mainstream epitaxial wafers used to make ⁇ LED need to undergo high-precision lithography, development, etching and other processes to separate the epitaxial materials. layer to form a single ⁇ LED chip unit. Due to the warpage and deformation of the epitaxial wafer, even if a high-precision lithography machine is used, the ideal chip size cannot be achieved, which ultimately seriously affects the overall production yield of the ⁇ LED single chip.
  • the traditional manufacturing method of ⁇ LED is: use MOCVD equipment to make epitaxial wafer of ⁇ LED structure on Si, SiC, Al 2 O 3 or GaN substrate, and then make the epitaxial wafer to form ⁇ LED chip through semiconductor processing technology, which involves photolithography , development, etching and bonding, substrate peeling, mass transfer of core particles, etc., the process is complicated and the yield is low.
  • the purpose of the present invention is to provide a method for fabricating a micro LED structure to improve the production yield, so as to solve the technical problem that the ideal chip size cannot be achieved even if a high-precision lithography machine is used.
  • the present invention provides a manufacturing method of a micro LED structure, comprising:
  • the patterned mask layer having openings exposing the substrate
  • epitaxial growth is performed on the substrate to form a micro LED structure at the opening; wherein, by controlling the projection of the opening in the plane direction of the substrate and the shape of the vertical section perpendicular to the substrate to control the optical properties of the micro-LED structure.
  • the optical performance includes a light exit direction; the opening gradually expands from the bottom wall to the opening;
  • the sidewall of the opening is flat, and the corresponding light-emitting direction of the micro-LED structure is a diverging beam;
  • the sidewall of the opening is a concave curved surface, and the corresponding light emitting direction of the micro LED structure is a parallel beam or a convergent beam;
  • the sidewall of the opening is an upwardly convex curved surface, and the corresponding light-emitting direction of the micro-LED structure is a divergent light beam.
  • the optical performance includes a beam projection shape; a vertical section of the opening in a direction perpendicular to the substrate is a rotationally symmetrical figure;
  • the projection of the opening in the plane direction of the substrate is circular, and the corresponding beam projection shape of the micro LED structure is circular;
  • the projection of the opening in the plane direction of the substrate is a polygon
  • the corresponding projection shape of the light beam of the micro LED structure is a polygon
  • the diameter of the opening ranges from 0.02 ⁇ m to 2 ⁇ m; the projection of the opening in the plane direction of the substrate is a polygon , the diameter of the circumscribed circle of the opening ranges from 0.02 ⁇ m to 2 ⁇ m.
  • a nucleation layer is formed on the substrate, the opening exposes the nucleation layer; and the micro LED structure is formed on the nucleation layer.
  • one of the micro LED structures is correspondingly formed at each of the openings.
  • At least two of the openings have different shapes of projections in the direction of the plane of the substrate, and/or have different shapes of vertical sections in the direction perpendicular to the substrate.
  • the plurality of openings are arranged according to a predetermined rule in a first direction and a second direction, and the first direction is perpendicular to the second direction.
  • the distance between adjacent openings ranges from 1 ⁇ m to 100 ⁇ m; and/or in the second direction, the distance between adjacent openings ranges from 1 ⁇ m to 100 ⁇ m. .
  • the ratio of the sum of the contact areas of the plurality of the micro LED structures with the substrate at the plurality of the openings to the total area of the substrate ranges from 0.01% to 5%.
  • the manufacturing method further includes:
  • the substrate is peeled off and the micro LED structure is transferred to the carrier.
  • a nucleation layer is formed on the substrate, and the opening exposes the nucleation layer; peeling off the substrate is replaced by peeling off the substrate and the substrate.
  • the nucleation layer is described.
  • the material of the nucleation layer is AlN
  • the material of the micro LED structure is a group III nitride-based material
  • the substrate and the nucleation layer are peeled off by laser.
  • the micro LED structure includes from bottom to top: a first type of semiconductor layer, a light-emitting layer and a second type of semiconductor layer, the first type of semiconductor layer and the second type of semiconductor layer are The conductivity type is opposite.
  • a patterned mask layer is formed on the substrate, and then epitaxial growth is performed.
  • epitaxial growth is performed.
  • the shape of the projection of the opening in the patterned mask layer in the plane direction of the substrate and the vertical substrate
  • the shape of the vertical section in the bottom direction so that during epitaxial growth, a micro LED structure with a specified shape and relatively independent space can be formed.
  • the above manufacturing method avoids the cutting process, and on the other hand, avoids the large-area growth of the LED epitaxial wafer and the resulting warpage deformation caused by the stress accumulation of the LED epitaxial wafer, thereby improving the yield of the micro LED structure.
  • micro-LED structures with different shapes have different optical properties, and the optical properties of micro-LED structures can be customized by controlling the opening shape.
  • the optical performance includes the light exit direction.
  • the opening gradually expands from the bottom wall to the opening; a) the side wall of the opening is flat, and the light emitting direction of the corresponding micro LED structure is a divergent beam. Or b) the side wall of the opening is a concave curved surface, and the light emitting direction of the corresponding micro LED structure is a parallel beam or a convergent beam. or c) the sidewall of the opening is an upwardly convex curved surface, and the light emitting direction of the corresponding micro LED structure is a divergent light beam. Can meet a variety of personalized needs.
  • the optical properties include the beam projection shape.
  • the vertical section of the opening in the direction perpendicular to the substrate is a rotationally symmetrical figure; a) The projection of the opening in the plane direction of the substrate is circular, and the beam projection shape of the corresponding micro LED structure is circular. or b) the projection of the opening in the plane direction of the substrate is a polygon, and the beam projection shape of the corresponding micro LED structure is a polygon. In other words, the projection of the opening in the plane direction of the substrate is consistent with the beam projection shape of the micro-LED structure.
  • a nucleation layer is formed on the substrate, and the opening exposes the nucleation layer; the micro LED structure formed at the opening includes a buffer layer adjacent to the nucleation layer.
  • the large-area growth of the buffer layer and the resulting continuous growth of defects in the buffer layer are avoided, and the quality of the subsequent epitaxial layer can be improved.
  • the buffer layer can be irradiated from the substrate by a laser of a specific wavelength to decompose it and become loose and porous, so that the substrate can be easily peeled off.
  • the manufacturing method further includes: using a carrier board to carry the micro-LED structure, etching and removing the patterned mask layer; peeling off the substrate, and transferring the micro-LED structure to the carrier board.
  • a carrier board to carry the micro-LED structure, etching and removing the patterned mask layer; peeling off the substrate, and transferring the micro-LED structure to the carrier board.
  • Various micro LED structures can be used individually.
  • the ratio of the sum of the contact areas of the plurality of micro LED structures with the substrate at the plurality of openings to the total area of the substrate ranges from 0.01% to 5%.
  • the small contact area makes it easy to separate the micro-LED structure from the substrate by laser lift-off or chemical etching; further, the stripped substrate has almost no loss, and can be repeatedly used in the fabrication of the micro-LED structure to achieve lining Zero consumption at the bottom.
  • FIG. 1 is a flow chart of a manufacturing method of a micro LED structure according to a first embodiment of the present invention
  • FIG. 2 to 4 are schematic diagrams of intermediate structures corresponding to the process in FIG. 1;
  • FIG. 5 and FIG. 6 are schematic diagrams of intermediate structures corresponding to the manufacturing method of the micro LED structure according to the second embodiment of the present invention.
  • FIG. 7 and 8 are schematic diagrams of intermediate structures corresponding to the manufacturing method of the micro LED structure according to the third embodiment of the present invention.
  • FIG. 9 is a schematic diagram of an intermediate structure corresponding to a manufacturing method of a micro LED structure according to a fourth embodiment of the present invention.
  • FIG. 10 and FIG. 11 are schematic diagrams of intermediate structures corresponding to the manufacturing method of the micro LED structure according to the fifth embodiment of the present invention.
  • the buffer layer 120 The buffer layer 120' after the reaction
  • FIG. 1 is a flow chart of a manufacturing method of a micro LED structure according to a first embodiment of the present invention
  • FIGS. 2 to 4 are schematic diagrams of intermediate structures corresponding to the flow in FIG. 1 .
  • a substrate 10 is provided, and a patterned mask layer 11 is formed on the substrate 10 . Opening 11a. 2 is a top view of the substrate and the patterned mask layer, and FIG. 3 is a cross-sectional view along the line AA in FIG. 2 .
  • the material of the substrate 10 may be sapphire, silicon carbide, silicon or diamond and other materials.
  • the material of the patterned mask layer 11 is an insulating material, such as silicon dioxide, silicon nitride, etc., which can be formed by physical vapor deposition or chemical vapor deposition, and patterned by dry etching or wet etching.
  • the thickness range of the patterned mask layer 11 may be: 0.1 ⁇ m ⁇ 10 ⁇ m.
  • the range includes endpoint values.
  • a nucleation layer 13 is further formed on the substrate 10 .
  • the opening 11a exposes the nucleation layer 13 .
  • the material of the nucleation layer 13 can be, for example, AlN, and the nucleation layer 13 can alleviate the problems of lattice mismatch and thermal mismatch between the epitaxially grown semiconductor layer, such as the first type semiconductor layer 12a and the substrate 10.
  • the opening 11a gradually expands from the bottom wall to the opening, and the side wall of the opening 11a is flat; the vertical section of the opening 11a in the direction perpendicular to the substrate 10 is a rotationally symmetrical figure, and the opening 11a is in the plane direction of the substrate 10.
  • the projection is circular.
  • the diameter of the opening 11a may range from 0.02 ⁇ m to 2 ⁇ m.
  • the plurality of openings 11a are arranged according to a predetermined rule in a first direction and a second direction, and the first direction and the second direction are perpendicular to each other.
  • the predetermined rule includes the array distribution in the row and column directions, that is, the first direction is the row direction, the second direction is the column direction, and the intersection of the rows and columns corresponds to an opening 11a.
  • the predetermined rule includes a staggered array distribution in the row and column directions, that is, on the basis of the array distribution in the row and column directions, the openings 11a at intervals of one row are moved up or down in the column direction by a predetermined distance, or the openings 11a at intervals of one column are moved in the row direction. Move up or down a predetermined distance.
  • the distance between adjacent openings 11 a may range from 1 ⁇ m to 100 ⁇ m; and/or in the second direction, the distance between adjacent openings 11 a may range from 1 ⁇ m to 100 ⁇ m.
  • the projected shapes of at least two openings 11 a in the plane direction of the substrate 10 are different, and/or the vertical cross-sections in the direction perpendicular to the substrate 10 are different.
  • the predetermined regularity of the arrangement of the plurality of openings 11a in the first direction and the second direction may include: the openings 11a of different shapes are alternately distributed.
  • the opening 11a may also have one.
  • step S2 in FIG. 1 , FIG. 3 and FIG. 4 using the patterned mask layer 11 as a mask, epitaxial growth is performed on the substrate 10 to form the micro LED structure 12 at the opening 11 a ; wherein , by controlling the shape of the projection of the opening 11 a in the plane direction of the substrate 10 and the shape of the vertical section in the direction perpendicular to the substrate 10 to control the optical performance of the micro LED structure 12 .
  • the micro LED structure 12 may include from bottom to top: a first type semiconductor layer 12a, a light emitting layer 12c and a second type semiconductor layer 12b, the first type semiconductor layer 12a and the second type semiconductor layer 12b have opposite conductivity types .
  • the semiconductor layer 12a of the first conductivity type may be an N-type semiconductor layer, and its material may be, for example, an N-type III-nitride-based material.
  • the N-type doping element may include at least one of Si, Ge, Sn, Se, or Te.
  • the Group III nitride-based material may include any one or a combination of GaN, AlGaN, InGaN, and AlInGaN.
  • a certain material is represented by a chemical element, but the molar ratio of each chemical element in the material is not limited.
  • GaN material contains Ga element and N element, but the molar ratio of Ga element and N element is not limited;
  • AlGaN material contains three elements, Al, Ga, and N, but the molar ratio of each is not limited.
  • the formation process of the N-type semiconductor layer may include: atomic layer deposition (ALD, Atomic layer deposition), or chemical vapor deposition (CVD, Chemical Vapor Deposition), or molecular beam epitaxy (MBE, Molecular Beam Epitaxy), or Plasma Enhanced Chemical Vapor Deposition (PECVD, Plasma Enhanced Chemical Vapor Deposition), or Low Pressure Chemical Vapor Deposition (LPCVD, Low Pressure Chemical Vapor Deposition), or Metal-Organic Chemical Vapor Deposition (MOCVD, Metal-Organic Chemical Vapor Deposition) ), or a combination thereof.
  • ALD Atomic layer deposition
  • CVD Chemical Vapor Deposition
  • MBE molecular beam epitaxy
  • PECVD Plasma Enhanced Chemical Vapor Deposition
  • LPCVD Low Pressure Chemical Vapor Deposition
  • MOCVD Metal-Organic Chemical Vapor Deposition
  • the N-type semiconductor layer may include one or more layers.
  • the light emitting layer 12c may include at least one of a single quantum well structure, a multiple quantum well (MQW) structure, a quantum wire structure, and a quantum dot structure.
  • the light emitting layer 12c may include a well layer and a barrier layer formed of a group III nitride-based material.
  • the Group III nitride-based material may include any one or a combination of GaN, AlGaN, InGaN, and AlInGaN.
  • the well layer may include an AlxGa1 - xN layer, where x is the percentage of the amount of Al element species to the sum of the amount of Al element and Ga element species, 1 ⁇ x ⁇ 0; and/or a barrier layer
  • An AlyGa1 -yN layer may be included, wherein y is the percentage of the amount of the Al element in the sum of the amount of the Al element and the Ga element, 1 ⁇ y ⁇ 0.
  • the forbidden band width of the well layer is smaller than that of the barrier layer.
  • the formation process of the well layer and/or the barrier layer may refer to the formation process of the N-type semiconductor layer.
  • the well layer and/or the barrier layer may or may not be doped with Al.
  • Undoping Al can improve its own crystal quality, but doping Al can improve the trapping probability of electrons in the well to improve the internal quantum efficiency.
  • Alternating multiple layers of well layers and barrier layers can form a multi-quantum well structure, which further improves the luminous efficiency.
  • the semiconductor layer 12b of the second conductivity type may be a P-type semiconductor layer, such as a P-type III-nitride-based material.
  • the P-type doping element may include at least one of Mg, Zn, Ca, Sr, or Ba.
  • the Group III nitride-based material may include any one or a combination of GaN, AlGaN, InGaN, and AlInGaN.
  • the formation process of the P-type semiconductor layer may refer to the formation process of the N-type semiconductor layer.
  • the P-type semiconductor layer may include one or more layers.
  • the P-type semiconductor layer may also be close to the substrate 10 , and the N-type semiconductor layer may be far away from the substrate 10 .
  • the buffer layer 120 is first epitaxially grown in the opening 11a.
  • the material of the buffer layer 120 may include at least one of GaN, AlGaN, and AlInGaN.
  • the buffer layer can reduce the dislocation density and defect density of the epitaxially grown semiconductor layer and improve the crystal quality.
  • the nucleation layer 13 and the buffer layer 120 are sequentially formed before the patterned mask layer 11 is formed on the substrate 10 .
  • the advantage of this embodiment is that the large-area growth of the buffer layer 120 and the resulting continuous growth of defects in the buffer layer 120 can be avoided, and the quality of subsequent epitaxial layers can be improved.
  • the micro LED structure 12 is not only formed in the opening 11 a, but also has a thickness higher than that of the patterned mask layer 11 .
  • the material of the mask layer 11 can be selected so that the second type semiconductor layer 12b is difficult to adhere to the patterned mask layer 11 .
  • the micro LED structures 12 are formed only within the openings 11a.
  • the above manufacturing method avoids the cutting process on the one hand, and avoids the large-area growth of the LED epitaxial wafer and the resulting warpage deformation caused by the stress accumulation of the LED epitaxial wafer, thereby improving the yield of the micro LED structure 12 .
  • the micro-LED structures 12 with different shapes have different optical properties, and the optical properties of the micro-LED structures 12 can be customized by controlling the shape of the opening 11a. For example, in this embodiment, since the sidewall of the opening 11a is flat, the light exit direction of the corresponding micro LED structure 12 is a diverging beam; since the projection of the opening 11a in the plane direction of the substrate 10 is circular, the corresponding micro LED The beam projection shape of the structure 12 is circular.
  • FIG. 5 and FIG. 6 are schematic diagrams of intermediate structures corresponding to the manufacturing method of the micro LED structure according to the second embodiment of the present invention.
  • the manufacturing method of the micro LED structure of the second embodiment is substantially the same as the manufacturing method of the micro LED structure of the first embodiment, the only difference is that in step S1 , referring to FIG. 5 , the opening 11 a in the patterned mask layer 11 is The sidewall of the LED is a concave curved surface; in step S2, as shown in FIG. 6 , the light-emitting direction of the epitaxially grown micro LED structure 12 is a parallel beam or a converging beam.
  • FIG. 7 and FIG. 8 are schematic diagrams of intermediate structures corresponding to the manufacturing method of the micro LED structure according to the third embodiment of the present invention.
  • the manufacturing method of the micro LED structure of the third embodiment is substantially the same as the manufacturing method of the micro LED structure of the first and second embodiments, and the difference is only that: in step S1, referring to FIG. 7 , in the patterned mask layer 11, the The sidewall of the opening 11a is an upwardly convex curved surface; in step S2 , as shown in FIG. 8 , the light emitting direction of the epitaxially grown micro LED structure 12 is a divergent light beam.
  • FIG. 9 is a schematic diagram of an intermediate structure corresponding to a manufacturing method of a micro LED structure according to a fourth embodiment of the present invention.
  • the fabrication method of the micro-LED structure of the fourth embodiment is substantially the same as the fabrication method of the micro-LED structure of the first, second, and third embodiments, the only difference being that in step S1, referring to FIG.
  • the projection in the plane direction is a polygon; in step S2, the beam projection shape of the epitaxially grown micro LED structure 12 is a polygon.
  • the diameter range of the circumscribed circle of the opening 11a may be 0.02 ⁇ m ⁇ 2 ⁇ m.
  • FIG. 10 and FIG. 11 are schematic diagrams of intermediate structures corresponding to the manufacturing method of the micro LED structure according to the fifth embodiment of the present invention.
  • the manufacturing method of the micro-LED structure of the fifth embodiment is substantially the same as the manufacturing method of the micro-LED structure of the first, second, third, and fourth embodiments, and the difference is only that: it also includes:
  • the carrier board 2 is used to carry the micro LED structure 12 , and the patterned mask layer 11 is etched and removed;
  • the substrate 10 is peeled off and the micro LED structures 12 are transferred to the carrier 2 .
  • the material of the patterned mask layer 11 is silicon dioxide, it is removed by etching with hydrofluoric acid; when the material of the patterned mask layer 11 is silicon nitride, it is removed by etching with hot phosphoric acid.
  • Laser lift-off is to irradiate the substrate 10 with laser light of certain wavelength bands, and the III-nitride-based material close to the substrate 10 will decompose nitrogen gas after absorbing the light of the above wavelength band, and become loose and porous for easy separation.
  • the substrate 10 is irradiated by a laser in the wavelength range of 200 nm to 300 nm.
  • the material of the nucleation layer 13 is an AlN layer, it is transparent to the light in the above wavelength band, but the buffer layer 120 will decompose nitrogen after absorbing the light in the above wavelength band.
  • the buffer layer after the reaction 120 ′ is loose and porous and easy to separate, so that the substrate 10 and the nucleation layer 13 can be easily peeled off without damaging the first type semiconductor layer 12 a.
  • Sapphire has a relatively high transmittance in the above-mentioned 200 nm-300 nm band, and can be used as a preferred material for the substrate 10 .
  • the chemical etching stripping is to use the etching solution to remove a certain crystal orientation of the substrate at a higher rate than other crystal orientations, so that the stripping can be achieved without fully etching the substrate 10.
  • one crystal direction of the horizontal plane may be [110]
  • the crystal direction of the thickness direction may be [111]
  • the etching solution may be a mixed solution of hydrofluoric acid, nitric acid and acetic acid. Since the removal rate of the etching solution in the [110] crystallographic direction is greater than the removal rate in the [111] crystallographic direction, the silicon substrate 10 can be separated from the micro LED structure 12 without being completely etched, and the rate of peeling the substrate 10 is accelerated.
  • substrate 10 materials such as sapphire, silicon carbide, diamond or GaN
  • targeted solutions can also be used for stripping.
  • the ratio of the sum of the contact areas of the plurality of micro LED structures 12 with the substrate 10 at the plurality of openings 11a to the total area of the substrate 10 may be 0.01%-5%.
  • the advantages are: the small contact area makes it easy to separate the micro LED structure 12 from the substrate 10 by laser lift-off or chemical etching; further, the stripped substrate 10 has almost no loss and can be used repeatedly for micro LEDs The fabrication of the structure 12 achieves zero consumption of the substrate 10 .

Abstract

一种微型LED结构（12）的制作方法，包括：提供衬底（10），在衬底（10）上形成图形化的掩膜层（11），图形化的掩膜层（11）具有暴露衬底（10）的开口（11a）；以图形化的掩膜层（11）为掩膜，对衬底（10）进行外延生长，以在开口（11a）处形成微型LED结构（12）；其中，通过控制开口（11a）在衬底（10）所在平面方向的投影的形状以及在垂直衬底（10）方向的竖剖面的形状以控制微型LED结构（12）的光学性能。微型LED结构（12）的制作方法一方面避免了切割工序，另一方面避免了大面积生长LED外延片以及由此导致的LED外延片应力积累产生翘曲变形，因而可提高微型LED结构（12）的良率。此外，不同形状的微型LED结构（12）具有不同的光学性能，通过开口（11a）形状控制可定制微型LED结构（12）的光学性能。

Description

微型LED结构的制作方法 技术领域
本申请涉及半导体技术领域，尤其涉及一种微型LED结构的制作方法。
背景技术
μLED(微型LED，尺寸小于＜50μm)尚处于研发阶段，截止到目前为止尚无实际商业量产化的μLED产品走向市场，影响μLED量产的一个重要因素是分割工艺。这是因为：
μLED单芯片尺寸的大小属于微米级，典型的μLED单芯粒尺寸为5μm*5μm，目前主流的用于制作μLED的外延片需经过高精度的光刻、显影、刻蚀等过程以分离外延材料层而形成单颗μLED芯粒单元。由于外延片存在翘曲变形从而造成即使使用高精度的光刻机也无法达到理想的芯片尺寸，最终严重影响μLED单芯片整体的制作良品率。μLED的传统制作方法为：在Si、SiC、Al 2O 3或者GaN衬底上使用MOCVD设备制作μLED结构的外延片，再通过半导体加工工艺将外延片制作形成μLED芯片，此加工工艺涉及光刻、显影、蚀刻以及键合、衬底剥离、芯粒巨量转移等，工艺过程复杂且良品率低下。
发明内容
本发明的发明目的是提供一种微型LED结构的制作方法，提高制作良品率，以解决即使使用高精度的光刻机也无法达到理想的芯片尺寸的技术问 题。
为实现上述目的，本发明提供一种微型LED结构的制作方法，包括：
提供衬底，在所述衬底上形成图形化的掩膜层，所述图形化的掩膜层具有暴露所述衬底的开口；
以所述图形化的掩膜层为掩膜，对所述衬底进行外延生长，以在所述开口处形成微型LED结构；其中，通过控制所述开口在所述衬底所在平面方向的投影的形状以及在垂直所述衬底方向的竖剖面的形状以控制所述微型LED结构的光学性能。
可选地，所述光学性能包括出光方向；所述开口自底壁向开口处逐渐膨大；
所述开口的侧壁呈平面，对应的所述微型LED结构的出光方向为发散光束；
或所述开口的侧壁呈下凹的曲面，对应的所述微型LED结构的出光方向为平行光束或汇聚光束；
或所述开口的侧壁呈上凸的曲面，对应的所述微型LED结构的出光方向为发散光束。
可选地，所述光学性能包括光束投影形状；所述开口在垂直所述衬底方向的竖剖面为旋转对称图形；
所述开口在所述衬底所在平面方向的投影呈圆形，对应的所述微型LED结构的光束投影形状为圆形；
或所述开口在所述衬底所在平面方向的投影呈多边形，对应的所述微型LED结构的光束投影形状为多边形。
可选地，所述开口在所述衬底所在平面方向的投影呈圆形时，所述开口的直径范围为：0.02μm～2μm；所述开口在所述衬底所在平面方向的投影 呈多边形时，所述开口的外接圆的直径范围为：0.02μm～2μm。
可选地，形成所述图形化的掩膜层前，在所述衬底上形成成核层，所述开口暴露所述成核层；在所述成核层上形成所述微型LED结构。
可选地，所述开口具有多个，对所述衬底进行外延生长时，每个所述开口处对应形成一个所述微型LED结构。
可选地，至少有两个所述开口在所述衬底所在平面方向的投影的形状不同，和/或在垂直所述衬底方向的竖剖面的形状不同。
可选地，在所述衬底所在平面上，所述多个开口在第一方向与第二方向上按预定规律排布，所述第一方向与所述第二方向垂直。
可选地，在所述第一方向上，相邻所述开口的间距范围为：1μm～100μm；和/或在所述第二方向上，相邻所述开口的间距范围为：1μm～100μm。
可选地，多个所述微型LED结构于多个所述开口处与所述衬底的接触面积总和与所述衬底的总面积的比值范围为：0.01％-5％。
可选地，所述制作方法还包括：
使用载板承载所述微型LED结构，腐蚀去除所述图形化的掩膜层；
剥离所述衬底，将所述微型LED结构转移至所述载板。
可选地，形成所述图形化的掩膜层前，在所述衬底上形成成核层，所述开口暴露所述成核层；剥离所述衬底替换为剥离所述衬底与所述成核层。
可选地，所述成核层的材料为AlN，所述微型LED结构的材料为Ⅲ族氮化物基材料，采用激光剥离所述衬底与所述成核层。
可选地，所述微型LED结构自下而上包括：第一类型的半导体层、发光层以及第二类型的半导体层，所述第一类型的半导体层与所述第二类型的半导体层的导电类型相反。
与现有技术相比，本发明的有益效果在于：
1)制造微型LED外延片之前，在衬底上形成图形化的掩膜层，再进行外延生长，通过控制图形化的掩膜层中开口在衬底所在平面方向的投影的形状以及在垂直衬底方向的竖剖面的形状，从而外延生长时，可形成具有指定形状且空间相对独立的微型LED结构。上述制作方法一方面避免了切割工序，另一方面避免了大面积生长LED外延片以及由此导致的LED外延片应力积累产生翘曲变形，因而可提高微型LED结构的良率。此外，不同形状的微型LED结构具有不同的光学性能，通过开口形状控制可定制微型LED结构的光学性能。
2)可选方案中，光学性能包括出光方向。开口自底壁向开口处逐渐膨大；a)开口的侧壁呈平面，对应的微型LED结构的出光方向为发散光束。或b)开口的侧壁呈下凹的曲面，对应的微型LED结构的出光方向为平行光束或汇聚光束。或c)开口的侧壁呈上凸的曲面，对应的微型LED结构的出光方向为发散光束。可满足各种个性化需求。
3)可选方案中，光学性能包括光束投影形状。开口在垂直衬底方向的竖剖面为旋转对称图形；a)开口在衬底所在平面方向的投影呈圆形，对应的微型LED结构的光束投影形状为圆形。或b)开口在衬底所在平面方向的投影呈多边形，对应的微型LED结构的光束投影形状为多边形。换言之，开口在衬底所在平面方向的投影与微型LED结构的光束投影形状一致。
4)可选方案中，形成图形化的掩膜层前，在衬底上形成成核层，开口暴露成核层；在开口处形成的微型LED结构包括临近成核层的缓冲层。避免了大面积生长缓冲层以及由此导致的缓冲层中缺陷延续生长，可提高后续外延层的质量。此外，可通过特定波长的激光自衬底照射缓冲层，使其分解，变得疏松多孔，轻易实现衬底剥离。
5)可选方案中，开口具有多个，对衬底进行外延生长时，每个开口处对应形成一个微型LED结构。一次外延生长工艺可形成大量的微型LED结构，有利于降低单个微型LED结构的成本。
6)可选方案中，制作方法还包括：使用载板承载微型LED结构，腐蚀去除图形化的掩膜层；剥离衬底，将微型LED结构转移至载板。各个微型LED结构可各自使用。
7)可选方案中，多个微型LED结构于多个开口处与衬底的接触面积总和与衬底的总面积的比值范围为：0.01％-5％。小的接触面积使得可以轻易地通过激光剥离或者化学腐蚀方式实现微型LED结构与衬底的分离；更一步地，剥离后的衬底几乎无损失，可反复用于微型LED结构的制作，实现衬底的零消耗。
附图说明
图1是本发明第一实施例的微型LED结构的制作方法的流程图；
图2至图4是图1中的流程对应的中间结构示意图；
图5与图6是本发明第二实施例的微型LED结构的制作方法对应的中间结构示意图；
图7与图8是本发明第三实施例的微型LED结构的制作方法对应的中间结构示意图；
图9是本发明第四实施例的微型LED结构的制作方法对应的中间结构示意图；
图10与图11是本发明第五实施例的微型LED结构的制作方法对应的中间结构示意图。
为方便理解本发明，以下列出本发明中出现的所有附图标记：
衬底10             图形化的掩膜层11
开口11a            微型LED结构12
缓冲层120                反应后的缓冲层120'
第一类型的半导体层12a    发光层12c
第二类型的半导体层12b    成核层13
载板2
具体实施方式
为使本发明的上述目的、特征和优点能够更为明显易懂，下面结合附图对本发明的具体实施例做详细的说明。
图1是本发明第一实施例的微型LED结构的制作方法的流程图；图2至图4是图1中的流程对应的中间结构示意图。
首先，参照图1中的步骤S1、图2以及图3所示，提供衬底10，在衬底10上形成图形化的掩膜层11，图形化的掩膜层11具有暴露衬底10的开口11a。其中，图2是衬底与图形化的掩膜层的俯视图，图3是沿着图2中的AA线的剖视图。
衬底10的材料可以为蓝宝石、碳化硅、硅或金刚石等材料。
图形化的掩膜层11的材料为绝缘材料，例如为二氧化硅、氮化硅等，可以采用物理气相沉积法或化学气相沉积法形成，采用干法刻蚀或湿法刻蚀图形化。
图形化的掩膜层11的厚度范围可以为：0.1μm～10μm。
需要说明的是，本实施例中，范围包括端点值。
本实施例中，在衬底10上还形成有成核层13。开口11a暴露成核层13。成核层13的材质可以例如为AlN，成核层13可以缓解外延生长的半导体层，例如第一类型的半导体层12a与衬底10之间的晶格失配和热失配的问 题。
本实施例中，开口11a自底壁向开口处逐渐膨大，开口11a的侧壁呈平面；开口11a在垂直衬底10方向的竖剖面为旋转对称图形，开口11a在衬底10所在平面方向的投影呈圆形。
开口11a的直径范围可以为：0.02μm～2μm。
此外，本实施例中，开口11a具有多个，且多个开口11a在衬底10所在平面方向的投影的形状相同，在垂直衬底10方向的竖剖面的形状相同。
在衬底10所在平面上，多个开口11a在第一方向与第二方向上按预定规律排布，第一方向与第二方向垂直。
一些实施例中，如图2所示，预定规律包括行列方向的阵列分布，即第一方向为行方向，第二方向行为列方向，行列交叉处对应一个开口11a。
一些实施例中，预定规律包括错位式行列方向的阵列分布，即在行列方向的阵列分布基础上，间隔一行的开口11a在列方向上移或下移预定距离，或间隔一列的开口11a在行方向上移或下移预定距离。
一个实施例中，在第一方向上，相邻开口11a的间距范围可以为：1μm～100μm；和/或在第二方向上，相邻开口11a的间距范围可以为：1μm～100μm。
一些实施例中，至少有两个开口11a在衬底10所在平面方向的投影的形状不同，和/或在垂直衬底10方向的竖剖面的不同。该些实施例中，多个开口11a在第一方向与第二方向上排布的预定规律可以包括：不同形状的开口11a交替分布。
一些实施例中，开口11a也可以具有一个。
接着，参照图1中的步骤S2、图3以及图4所示，以图形化的掩膜层11为掩膜，对衬底10进行外延生长，以在开口11a处形成微型LED结构12； 其中，通过控制开口11a在衬底10所在平面方向的投影的形状以及在垂直衬底10方向的竖剖面的形状以控制微型LED结构12的光学性能。
微型LED结构12自下而上可以包括：第一类型的半导体层12a、发光层12c以及第二类型的半导体层12b，第一类型的半导体层12a与第二类型的半导体层12b的导电类型相反。
第一导电类型的半导体层12a可以为N型半导体层，其材料例如可以为N型Ⅲ族氮化物基材料。N型掺杂元素可以包括Si、Ge、Sn、Se或Te中的至少一种。Ⅲ族氮化物基材料可以包括GaN、AlGaN、InGaN、AlInGaN中的任一种或组合。
需要说明的是，本实施例中，以化学元素代表某种材料，但不限定该材料中各化学元素的摩尔占比。例如GaN材料中，包含Ga元素与N元素，但不限定Ga元素与N元素的摩尔占比；AlGaN材料中，包含Al、Ga、N三种元素，但不限定各自的摩尔占比大小。
N型半导体层的形成工艺可以包括：原子层沉积法(ALD，Atomic layer deposition)、或化学气相沉积法(CVD，Chemical Vapor Deposition)、或分子束外延生长法(MBE，Molecular Beam Epitaxy)、或等离子体增强化学气相沉积法(PECVD，Plasma Enhanced Chemical Vapor Deposition)、或低压化学蒸发沉积法(LPCVD，Low Pressure Chemical Vapor Deposition)，或金属有机化合物化学气相沉积法(MOCVD，Metal-Organic Chemical Vapor Deposition)、或其组合方式。
N型半导体层可以包括一层或多层。
发光层12c可以包括单量子阱结构、多量子阱(MQW)结构、量子线结构和量子点结构中的至少一种。发光层12c可以包括Ⅲ族氮化物基材料形成的阱层和势垒层。Ⅲ族氮化物基材料可以包括GaN、AlGaN、InGaN、AlInGaN中的任一种或组合。
例如，阱层可以包括Al xGa 1-xN层，其中x为Al元素的物质的量占Al元素与Ga元素物质的量之和的百分比，1≥x≥0；和/或势垒层可以包括Al yGa 1-yN层，其中y为Al元素的物质的量占Al元素与Ga元素物质的量之和的百分比，1≥y≥0。阱层的禁带宽度小于势垒层的禁带宽度。
阱层和/或势垒层的形成工艺可以参照N型半导体层的形成工艺。
阱层和/或势垒层可以掺杂Al，也可以不掺杂Al。不掺杂Al可以提高自身结晶质量，但是掺杂Al可以提升阱对电子的俘获几率以提升内量子效率。
阱层和势垒层多层交替可以形成多量子阱结构，进一步提高发光效率。
第二导电类型的半导体层12b可以为P型半导体层，例如P型Ⅲ族氮化物基材料。P型掺杂元素可以包括Mg、Zn、Ca、Sr或Ba中的至少一种。Ⅲ族氮化物基材料可以包括GaN、AlGaN、InGaN、AlInGaN中的任一种或组合。
P型半导体层的形成工艺可以参照N型半导体层的形成工艺。
P型半导体层可以包括一层或多层。
一些实施例中，也可以P型半导体层靠近衬底10，N型半导体层远离衬底10。
本实施例中，外延生长第一类型的半导体层12a之前，在开口11a内先外延生长缓冲层120。缓冲层120的形成方法可以参照第一类型的半导体层12a的形成方法。缓冲层120的材质可以包括GaN、AlGaN、AlInGaN中的至少一种。缓冲层可以降低外延生长的半导体层的位错密度和缺陷密度，提升晶体质量。
其它实施例中，在衬底10上形成图形化的掩膜层11之前，先依次形成成核层13与缓冲层120。相对于该实施例，本实施例的好处在于：可避免大面积生长缓冲层120以及由此导致的缓冲层120中缺陷延续生长，可提高后续外延层的质量。
本实施例中，微型LED结构12不仅形成在开口11a内，厚度还可高于图形化的掩膜层11的厚度。可通过掩膜层11的材料选择，使得第二类型的半导体层12b难以附着在图形化的掩膜层11上。
一些实施例中，微型LED结构12仅形成在开口11a内。
上述制作方法一方面避免了切割工序，另一方面避免了大面积生长LED外延片以及由此导致的LED外延片应力积累产生翘曲变形，因而可提高微型LED结构12的良率。此外，不同形状的微型LED结构12具有不同的光学性能，通过开口11a形状控制可定制微型LED结构12的光学性能。例如本实施例中，由于开口11a的侧壁呈平面，因而对应的微型LED结构12的出光方向为发散光束；由于开口11a在衬底10所在平面方向的投影呈圆形，因而对应的微型LED结构12的光束投影形状为圆形。
图5与图6是本发明第二实施例的微型LED结构的制作方法对应的中间结构示意图。
本实施例二的微型LED结构的制作方法与实施例一的微型LED结构的制作方法大致相同，区别仅在于：步骤S1中，参照图5所示，图形化的掩膜层11中的开口11a的侧壁呈下凹的曲面；步骤S2中，参照图6所示，外延生长的微型LED结构12的出光方向为平行光束或汇聚光束。
图7与图8是本发明第三实施例的微型LED结构的制作方法对应的中间结构示意图。
本实施例三的微型LED结构的制作方法与实施例一、二的微型LED结构的制作方法大致相同，区别仅在于：步骤S1中，参照图7所示，图形化的掩膜层11中的开口11a的侧壁呈上凸的曲面；步骤S2中，参照图8所示，外延生长的微型LED结构12的出光方向为发散光束。
图9是本发明第四实施例的微型LED结构的制作方法对应的中间结构示意图。
本实施例四的微型LED结构的制作方法与实施例一、二、三的微型LED结构的制作方法大致相同，区别仅在于：步骤S1中，参照图9所示，开口11a在衬底10所在平面方向的投影呈多边形；步骤S2中，外延生长的微型LED结构12的光束投影形状为多边形。
开口11a的外接圆的直径范围可以为：0.02μm～2μm。
图10与图11是本发明第五实施例的微型LED结构的制作方法对应的中间结构示意图。
本实施例五的微型LED结构的制作方法与实施例一、二、三、四的微型LED结构的制作方法大致相同，区别仅在于：还包括：
参照图10与图11所示，使用载板2承载微型LED结构12，腐蚀去除图形化的掩膜层11；
剥离衬底10，将微型LED结构12转移至载板2。
当图形化的掩膜层11的材料为二氧化硅时，采用氢氟酸腐蚀去除；当图形化的掩膜层11的材料为氮化硅时，采用热磷酸腐蚀去除。
衬底10的剥离方式包括两种：激光剥离与化学腐蚀剥离。
激光剥离是利用某些波段的激光照射衬底10，靠近衬底10的Ⅲ族氮化物基材料吸收上述波段的光后会分解出氮气，变得疏松多孔易分离。
例如200nm～300nm波段的激光照射衬底10，成核层13的材料为AlN层时，对上述波段的光透明，但缓冲层120吸收上述波段的光后会分解出氮气，反应后的缓冲层120'疏松多孔易分离，从而可方便地剥离衬底10与成核层13，且不会损伤第一类型的半导体层12a。
蓝宝石在上述200nm～300nm波段的透光率较高，可作为衬底10的优选材料。
化学腐蚀剥离是利用腐蚀液对衬底的某一晶向的去除速率大于其它晶 向的去除速率，以无需全部腐蚀衬底10即可实现剥离。
例如当衬底10的材料为单晶硅时，水平面的一个晶向可以为[110]，厚度方向的晶向可以为[111]，腐蚀液可以为氢氟酸、硝酸、乙酸的混和液。由于腐蚀液在[110]晶向的去除速率大于在[111]晶向的去除速率，因而，硅衬底10无需全部腐蚀即可脱离微型LED结构12，加快了剥离衬底10的速率。
对于其它的衬底10材料，例如蓝宝石、碳化硅、金刚石或GaN，也可采用针对性的溶液进行剥离。
一些实施例中，多个微型LED结构12于多个开口11a处与衬底10的接触面积总和与衬底10的总面积的比值范围可以为：0.01％-5％。好处在于：小的接触面积使得可以轻易地通过激光剥离或者化学腐蚀方式实现微型LED结构12与衬底10的分离；更一步地，剥离后的衬底10几乎无损失，可反复用于微型LED结构12的制作，实现衬底10的零消耗。
虽然本发明披露如上，但本发明并非限定于此。任何本领域技术人员，在不脱离本发明的精神和范围内，均可作各种更动与修改，因此本发明的保护范围应当以权利要求所限定的范围为准。

Claims (12)

  1. 一种微型LED结构的制作方法，其特征在于，包括：
    提供衬底(10)，在所述衬底(10)上形成图形化的掩膜层(11)，所述图形化的掩膜层(11)具有暴露所述衬底(10)的开口(11a)；
    以所述图形化的掩膜层(11)为掩膜，对所述衬底(10)进行外延生长，以在所述开口(11a)处形成微型LED结构(12)；其中，通过控制所述开口(11a)在所述衬底(10)所在平面方向的投影的形状以及在垂直所述衬底(10)方向的竖剖面的形状以控制所述微型LED结构(12)的光学性能。
  2. 根据权利要求1所述的微型LED结构的制作方法，其特征在于，所述光学性能包括出光方向；所述开口(11a)自底壁向开口处逐渐膨大；
    所述开口(11a)的侧壁呈平面，对应的所述微型LED结构(12)的出光方向为发散光束；
    或所述开口(11a)的侧壁呈下凹的曲面，对应的所述微型LED结构(12)的出光方向为平行光束或汇聚光束；
    或所述开口(11a)的侧壁呈上凸的曲面，对应的所述微型LED结构(12)的出光方向为发散光束。
  3. 根据权利要求1所述的微型LED结构的制作方法，其特征在于，所述光学性能包括光束投影形状；所述开口(11a)在垂直所述衬底(10)方向的竖剖面为旋转对称图形；
    所述开口(11a)在所述衬底(10)所在平面方向的投影呈圆形，对应的所述微型LED结构(12)的光束投影形状为圆形；
    或所述开口(11a)在所述衬底(10)所在平面方向的投影呈多边形，对应的所述微型LED结构(12)的光束投影形状为多边形。
  4. 根据权利要求1所述的微型LED结构的制作方法，其特征在于，所述开口(11a)在所述衬底(10)所在平面方向的投影呈圆形时，所述开口(11a)的直径范围为：0.02μm～2μm；所述开口(11a)在所述衬底(10)所在平 面方向的投影呈多边形时，所述开口(11a)的外接圆的直径范围为：0.02μm～2μm。
  5. 根据权利要求1所述的微型LED结构的制作方法，其特征在于，形成所述图形化的掩膜层(11)前，在所述衬底(10)上形成成核层(13)，所述开口(11a)暴露所述成核层(13)；在所述成核层(13)上形成所述微型LED结构(12)。
  6. 根据权利要求1所述的微型LED结构的制作方法，其特征在于，所述开口(11a)具有多个，对所述衬底(10)进行外延生长时，每个所述开口(11a)处对应形成一个所述微型LED结构(12)。
  7. 根据权利要求6所述的微型LED结构的制作方法，其特征在于，至少有两个所述开口(11a)在所述衬底(10)所在平面方向的投影的形状不同，和/或在垂直所述衬底(10)方向的竖剖面的形状不同。
  8. 根据权利要求6所述的微型LED结构的制作方法，其特征在于，在所述衬底(10)所在平面上，所述多个开口(11a)在第一方向与第二方向上按预定规律排布，所述第一方向与所述第二方向垂直。
  9. 根据权利要求8所述的微型LED结构的制作方法，其特征在于，在所述第一方向上，相邻所述开口(11a)的间距范围为：1μm～100μm；和/或在所述第二方向上，相邻所述开口(11a)的间距范围为：1μm～100μm。
  10. 根据权利要求6所述的微型LED结构的制作方法，其特征在于，多个所述微型LED结构(12)于多个所述开口(11a)处与所述衬底(10)的接触面积总和与所述衬底(10)的总面积的比值范围为：0.01％-5％。
  11. 根据权利要求1所述的微型LED结构的制作方法，其特征在于，还包括：
    使用载板(2)承载所述微型LED结构(12)，腐蚀去除所述图形化的掩膜层(11)；
    剥离所述衬底(10)，将所述微型LED结构(12)转移至所述载板(2)。
  12. 根据权利要求11所述的微型LED结构的制作方法，其特征在于，形 成所述图形化的掩膜层(11)前，在所述衬底(10)上形成成核层(13)，所述开口(11a)暴露所述成核层(13)；剥离所述衬底(10)替换为剥离所述衬底(10)与所述成核层(13)。
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