CN114203874A - A patterned composite substrate, preparation method and LED epitaxial wafer - Google Patents
A patterned composite substrate, preparation method and LED epitaxial wafer Download PDFInfo
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- CN114203874A CN114203874A CN202010979348.5A CN202010979348A CN114203874A CN 114203874 A CN114203874 A CN 114203874A CN 202010979348 A CN202010979348 A CN 202010979348A CN 114203874 A CN114203874 A CN 114203874A
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- H—ELECTRICITY
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- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
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- H10H20/819—Bodies characterised by their shape, e.g. curved or truncated substrates
- H10H20/82—Roughened surfaces, e.g. at the interface between epitaxial layers
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- G—PHYSICS
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- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
- G03F1/76—Patterning of masks by imaging
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- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/01—Manufacture or treatment
- H10H20/011—Manufacture or treatment of bodies, e.g. forming semiconductor layers
- H10H20/013—Manufacture or treatment of bodies, e.g. forming semiconductor layers having light-emitting regions comprising only Group III-V materials
- H10H20/0133—Manufacture or treatment of bodies, e.g. forming semiconductor layers having light-emitting regions comprising only Group III-V materials with a substrate not being Group III-V materials
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- H—ELECTRICITY
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- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/01—Manufacture or treatment
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- H10H20/013—Manufacture or treatment of bodies, e.g. forming semiconductor layers having light-emitting regions comprising only Group III-V materials
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Abstract
本发明实施例公开了一种图形化复合衬底、制备方法及LED外延片。该图形化复合衬底的制备方法包括：在衬底基板上形成第一异质层；在第一异质层上形成第二异质层，第二异质层中掺杂有硼、磷或锗中的至少一种元素；对第二异质层进行高温退火平坦化处理；在第二异质层表面形成光刻胶层；通过图形转移技术，使光刻胶层形成光刻胶胶柱掩膜；根据光刻胶胶柱掩膜，对第二异质层、第一异质层和衬底基板进行图形化，形成图形化复合衬底。本发明实施例解决了现有的异质层表面平坦度低和粗糙度差的问题，能够制备形成符合标准的图形化复合衬底，有利于改善外延层生长质量，同时保证图形化复合衬底对光线路径的改善，提高LED芯片的光出射效率。
The embodiments of the present invention disclose a patterned composite substrate, a preparation method and an LED epitaxial wafer. The preparation method of the patterned composite substrate comprises: forming a first hetero layer on a base substrate; forming a second hetero layer on the first hetero layer, and the second hetero layer is doped with boron, phosphorus or at least one element in germanium; perform high-temperature annealing and planarization treatment on the second hetero layer; form a photoresist layer on the surface of the second hetero layer; use pattern transfer technology to form a photoresist column from the photoresist layer mask; patterning the second heterogeneous layer, the first heterogeneous layer and the base substrate according to the photoresist column mask to form a patterned composite substrate. The embodiment of the present invention solves the problems of low flatness and poor roughness of the existing hetero layer surface, can prepare and form a patterned composite substrate that meets the standard, is beneficial to improve the growth quality of the epitaxial layer, and at the same time ensures the patterned composite substrate The improvement of the light path improves the light output efficiency of the LED chip.
Description
Technical Field
The embodiment of the invention relates to the technical field of semiconductor manufacturing, in particular to a graphical composite substrate, a preparation method and an LED epitaxial wafer.
Background
Composite patterned substrate (e.g. SiO)2/Al2O3) The crystal quality and the light extraction efficiency of the GaN-based LED device can be further improved. First aspect, SiO2/Al2O3Composite patterned substrate due to SiO2The material is not suitable for GaN to grow on, so that dislocation can be promoted to bend along the side face of the graph and fold at the top of the graph, and the crystal quality of the GaN material is improved; second aspect, SiO2/Al2O3SiO in composite patterned substrates2The material has larger refractive index difference with the GaN material, and the total reflection angle formed by the material and the GaN material is larger, so that the light extraction efficiency can be improved; in the third aspect, the composite patterned substrate is mainly a silicon dioxide layer by dry etching, and the dry etching rate is higher than that of sapphire, so that the etching time can be greatly reduced, the capacity of etching equipment is improved, and the production cost is reduced.
However, in conventional patterned composite substrate flows, heterogeneous layers (SiO) are prepared using Plasma Enhanced Chemical Vapor Deposition (PECVD) or magnetron sputtering2) The surface flatness and roughness of the film are poor, the surface defects are more, the preparation of a photoetching mask and etching at the rear end are adversely affected, and chromatic aberration and micro defects are easily caused. And, a heterogeneous layer (SiO)2) The thickness of the film is low, and the conventional polishing process cannot accurately realize the surface planarization treatment. In addition, wafer chipping is prone to occur due to stress issues with the substrate and the coating material.
Disclosure of Invention
The invention provides a graphical composite substrate, a preparation method and an LED epitaxial wafer, which aim to improve the flatness and the roughness of a heterogeneous layer in the graphical composite substrate and improve the graphical accuracy of the graphical composite substrate.
In a first aspect, an embodiment of the present invention provides a method for preparing a patterned composite substrate, including:
forming a first heterogeneous layer on a substrate;
forming a second heterogeneous layer on the first heterogeneous layer, wherein the second heterogeneous layer is doped with at least one element of boron, phosphorus or germanium;
carrying out high-temperature annealing planarization treatment on the second heterogeneous layer;
forming a photoresist layer on the surface of the second heterogeneous layer;
forming a photoresist column mask on the photoresist layer by a pattern transfer technology;
and patterning the second heterogeneous layer, the first heterogeneous layer and the substrate base plate according to the photoresist column mask to form a patterned composite substrate.
Optionally, the doping proportion of boron, phosphorus or germanium in the second heterogeneous layer ranges from 0 wt% to 5 wt%.
Optionally, the thickness of the second heterogeneous layer accounts for a proportion range of 10% -20% of the sum of the thicknesses of the first heterogeneous layer and the second heterogeneous layer.
Optionally, the temperature condition range of the high-temperature annealing planarization treatment is 800-.
Optionally, the patterned composite substrate comprises the substrate base plate and a plurality of heterogeneous raised microstructures located on the substrate base plate;
the heterogeneous raised microstructures are made of the same material as the first heterogeneous layer; or the heterogeneous raised microstructure comprises an upper layer structure and a lower layer structure which are mutually stacked, the upper layer structure and the second heterogeneous layer are made of the same material, and the lower layer structure and the first heterogeneous layer are made of the same material.
Optionally, the patterned composite substrate includes the substrate base plate and a patterned heterogeneous layer located on the substrate base plate, a plurality of microstructure cavities are formed on the surface of the patterned heterogeneous layer, and the microstructure cavities penetrate through the patterned heterogeneous layer;
the patterned heterogeneous layer and the first heterogeneous layer are made of the same material; or, the patterned heterogeneous layer comprises an upper layer structure and a lower layer structure, the upper layer structure is the same as the second heterogeneous layer in material, and the lower layer structure is the same as the first heterogeneous layer in material.
Optionally, the heterogeneous material used in the first heterogeneous layer and the second heterogeneous layer includes at least one of oxide, nitride, and carbide.
Optionally, the heterogeneous material used in the first heterogeneous layer and the second heterogeneous layer includes at least one of silicon oxide, titanium oxide, silicon nitride, and silicon carbide.
Optionally, the photoresist layer has a thickness in a range of 0.3 μm to 5 μm.
In a second aspect, an embodiment of the present invention further provides a patterned composite substrate, which is prepared by using the preparation method according to any one of the first aspect.
In a third aspect, the embodiment of the invention further provides an LED epitaxial wafer, which includes the patterned composite substrate according to the second aspect.
According to the patterned composite substrate, the preparation method and the LED epitaxial wafer provided by the embodiment of the invention, the first heterogeneous layer is formed on the substrate base plate, and then the second heterogeneous layer is formed on the first heterogeneous layer, wherein the second heterogeneous layer is doped with at least one element of boron, phosphorus or germanium; and finally, patterning the second heterogeneous layer, the first heterogeneous layer and the substrate according to the photoresist column mask to form a patterned composite substrate. The embodiment of the invention solves the problems of low surface flatness and poor roughness of the existing heterogeneous layer, can prepare and form the photoresist layer with smaller size error and the photoresist column mask by utilizing the second heterogeneous layer, and can prepare and form the patterned composite substrate which meets the standard, thereby being beneficial to the patterned composite substrate to improve the growth quality of the epitaxial layer, simultaneously ensuring the improvement of the patterned composite substrate on the light path and improving the light emitting efficiency of the LED chip. The preparation method has simple and easily-obtained flow, can ensure that the pattern size in the patterned composite substrate meets the requirement through a one-step coating process and a one-step heat treatment process, and reduces the pattern error caused by the process.
Drawings
Fig. 1 is a flowchart of a method for manufacturing a patterned composite substrate according to an embodiment of the present invention;
FIG. 2 is a structural flow diagram of a method of making the patterned composite substrate of FIG. 1;
FIG. 3 is a schematic structural diagram of another patterned composite substrate provided by embodiments of the present invention;
FIGS. 4 and 5 are schematic structural diagrams of two further patterned composite substrates provided by embodiments of the present invention;
fig. 6 is a schematic structural diagram of an LED epitaxial wafer according to an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention. It should be further noted that, for the convenience of description, only some of the structures related to the present invention are shown in the drawings, not all of the structures.
Fig. 1 is a flowchart of a method for manufacturing a patterned composite substrate according to an embodiment of the present invention, fig. 2 is a flowchart of a structure of the method for manufacturing the patterned composite substrate shown in fig. 1, and referring to fig. 1 and fig. 2, the method for manufacturing the patterned composite substrate includes:
s110, forming a first heterogeneous layer on a substrate;
referring to fig. 2 a), the substrate 10 is a substrate that is polished smoothly and has a flat surface, i.e. the substrate has a good quality C-plane, which can help the epitaxial crystal form nuclei and grow into an epitaxial layer. The substrate may be a sapphire substrate, and the like, without limitation. The first hetero layer 21 is a film made of a hetero material which is substantially different from the substrate 10 and the epitaxial layer material, such as gallium nitride, with respect to the substrate 10 and the epitaxial layer material. The growth of the epitaxial material on the heterogeneous material is difficult, namely the heterogeneous material has the function of inhibiting the growth of the epitaxial material.
The first heterogeneous layer 21 may be a heterogeneous layer, i.e., a film layer formed on the substrate 10 using one material, or a plurality of film layers formed on the substrate sequentially using a plurality of materials. It is understood that, in order to realize the sequential gradual change or abrupt change of the refractive index in the patterned composite substrate prepared subsequently, a plurality of film layers of heterogeneous materials with different refractive indexes can be disposed in the first heterogeneous layer 21, which is not limited herein.
S120, forming a second heterogeneous layer on the first heterogeneous layer, wherein the second heterogeneous layer is doped with at least one element of boron, phosphorus or germanium;
referring to fig. 2 b), the second hetero-layer 22 is also made of a hetero-material. In contrast to the first heterostructure layer 21, the second heterostructure layer 22 is doped with other elements. The heterogeneous layer material doped with boron, phosphorus or germanium elements has flowability at high temperature, and the second heterogeneous layer 22 is doped with a proper amount of at least one of the three elements, so that the heterogeneous layer (including the first heterogeneous layer 21 and the second heterogeneous layer 22) formed on the substrate 10 has better pore filling capability and can have a flatter surface. Meanwhile, compared with the undoped heterogeneous layer, the second heterogeneous layer 22 doped with the three elements has smaller film stress, can reduce the problem of cracking caused by a coating process, and can avoid the crack defect on the surface of the heterogeneous layer.
Specifically, the heterogeneous material used in the first heterogeneous layer 21 and the second heterogeneous layer 22 may specifically include at least one of an oxide, a nitride, and a carbide, and may be, for example, silicon oxide, titanium oxide, silicon nitride, and silicon carbide. In the above steps S110 and S120, the first heterogeneous layer 21 and the second heterogeneous layer 22 can be prepared by using a chemical vapor deposition, a magnetron sputtering process, etc., in case that the heterogeneous materials in the first heterogeneous layer 21 and the second heterogeneous layer 22 are both silicon dioxide.
S130, carrying out high-temperature annealing planarization treatment on the second heterogeneous layer;
referring to fig. 2 c), this step is essentially a process of planarizing the second heterogeneous layer 22 by a high temperature annealing process. In the high-temperature annealing process, the second heterogeneous layer 22 doped with boron, phosphorus or germanium elements has stronger fluidity and better filling capacity, so that the surface is smoother and denser, and the roughness is reduced.
Specifically, the temperature condition range for the high temperature annealing planarization treatment in the step can be set to 800-.
S140, forming a photoresist layer on the surface of the second heterogeneous layer;
referring to d) of fig. 2, since the second heterogeneous layer 22 is planarized, the photoresist layer 30 formed on the planarized surface thereof is also more planarized and has a more uniform thickness. Specifically, in preparing the photoresist layer 30, the photoresist may be selected as a positive photoresist or a negative photoresist. The photoresist layer 30 may be prepared by a spin coating or spray coating process, and may have a thickness ranging from 0.3 μm to 5 μm.
S150, forming a photoresist column mask on the photoresist layer by a pattern transfer technology;
referring to fig. 2 e), the photoresist column mask 31 is a pattern mask for patterning the second and first heterogeneous layers and the substrate, and the pattern of the photoresist column mask 31 corresponds to the pattern finally formed on the patterned composite substrate. The photoresist column mask 31 can be fabricated by a pattern transfer technique such as photolithography or nanoimprint. Taking a photolithography process as an example, the photoresist layer 30 is exposed through a photolithography mask, and then the photoresist layer 30 is patterned by a developing step, that is, the pattern of the photolithography mask is transferred onto the photoresist layer 30 to form a photoresist column mask 31.
And S160, patterning the second heterogeneous layer, the first heterogeneous layer and the substrate base plate according to the photoresist column mask to form a patterned composite substrate.
Referring to f) of fig. 2, the step is a process of performing pattern transfer according to the photoresist column mask, and specifically, the patterning of the second heterogeneous layer, the first heterogeneous layer and the substrate can be completed by etching using a dry or wet etching process. Exemplarily, fig. 2 f) is a schematic structural diagram of a patterned composite substrate provided by an embodiment of the present invention, which may include a substrate base plate 10 and a plurality of heterogeneous protruding microstructures 50 located on the substrate base plate 10; the heterogeneous raised microstructures 50 are of the same material as the first heterogeneous layer 21. In other words, in the final patterned composite substrate, the hetero-convex microstructures 50 are mainly formed by patterning the first hetero-layer 21, and the second hetero-layer 22 is removed during the patterning process. The shape of the heterogeneous convex microstructure 50 may be a cone structure, a columnar structure or a platform-shaped structure, and specifically may be a polygonal cone, a cone, an elliptical cone, a polygonal cylinder, a cylinder, an elliptical cylinder, a polygonal platform-shaped structure, a circular platform, an elliptical platform-shaped structure, and the like, which is not limited herein.
It is understood that due to the disposition of the second heterogeneous layer 22, the surface of the photoresist layer 30 formed thereon is more flat and the thickness is more uniform, so that the photoresist pillar mask formed in step S150 is more accurately patterned, wherein the size of the photoresist pillar is more in accordance with the standard. And then, the finally formed patterned composite substrate formed by using the photoresist gel column mask is more standard and has smaller size error, and the finally formed patterned composite substrate can better optimize the growth condition of epitaxial materials, improve the light emergent path and improve the light emergent efficiency.
According to the preparation method of the patterned composite substrate and the patterned composite substrate provided by the embodiment of the invention, the first heterogeneous layer is formed on the substrate base plate, and then the second heterogeneous layer is formed on the first heterogeneous layer, wherein the second heterogeneous layer is doped with at least one element of boron, phosphorus or germanium; and finally, patterning the second heterogeneous layer, the first heterogeneous layer and the substrate according to the photoresist column mask to form a patterned composite substrate. The embodiment of the invention solves the problems of low surface flatness and poor roughness of the existing heterogeneous layer, can prepare and form the photoresist layer with smaller size error and the photoresist column mask by utilizing the second heterogeneous layer, and can prepare and form the patterned composite substrate which meets the standard, thereby being beneficial to the patterned composite substrate to improve the growth quality of the epitaxial layer, simultaneously ensuring the improvement of the patterned composite substrate on the light path and improving the light emitting efficiency of the LED chip. The preparation method has simple and easily-obtained flow, can ensure that the pattern size in the patterned composite substrate meets the requirement through a one-step coating process and a one-step heat treatment process, and reduces the pattern error caused by the process.
In the method for preparing the patterned composite substrate, the second heterogeneous layer 22 doped with boron, phosphorus or germanium elements may be doped with one element or a combination of two or more elements. The doping of the above elements is only for the purpose of planarizing the surface of the heterogeneous layer formed on the substrate 10, reducing the stress of the film layer, and avoiding cracking. Therefore, when the second heterogeneous layer 22 is disposed, it is preferably disposed with a thinner thickness, and the first heterogeneous layer 21 has a thicker thickness, and in the patterned composite substrate formed later, the first heterogeneous layer 21 is mainly used for forming heterogeneous structures in the patterned composite substrate, and the second heterogeneous layer 22 can be removed in the patterning process. The embodiment of the invention provides specific thickness proportion of the first heterogeneous layer and the second heterogeneous layer aiming at the actual process. Alternatively, the thickness of the second hetero layer 22 may be set to a ratio ranging from 10% to 20% of the sum of the thicknesses of the first hetero layer 21 and the second hetero layer.
In addition, considering that the refractive index of the second hetero layer 22 is changed by doping with boron, phosphorus or germanium element, the refractive index of the second hetero layer 22 is generally increased. In order to avoid the influence of the refractive index difference on the light path and the reduction of the light extraction efficiency when the second heterogeneous layer 22 and the first heterogeneous layer 21 form the patterned structure in the patterned composite substrate, the content of boron, phosphorus or germanium doped in the second heterogeneous layer 22 can be controlled within the range of 0 wt% to 5 wt%. At this time, the doping content of the elements in the second hetero layer 22 is low, and the influence on the refractive index is small, and the doping content can also satisfy the requirement of planarization of the second hetero layer 22, so that the second hetero layer 22 with low surface roughness is formed.
Based on the above, the embodiment of the invention also provides a patterned composite substrate. Fig. 3 is a schematic structural diagram of another patterned composite substrate according to an embodiment of the present invention, and referring to fig. 3, alternatively, in the patterned composite substrate, the heterogeneous raised microstructure 50 includes an upper structure 51 and a lower structure 52 stacked on each other, the upper structure 51 is of the same material as the second heterogeneous layer, and the lower structure 52 is of the same material as the first heterogeneous layer. In other words, in the step S160 of patterning the second heterogeneous layer, the first heterogeneous layer and the substrate according to the photoresist column mask to form the patterned composite substrate, in the composite substrate formed by patterning, the first heterogeneous layer and the second heterogeneous layer are simultaneously patterned, and they collectively form the heterogeneous protruding microstructure. Obviously, the upper layer structure of the heterogeneous raised microstructure is substantially doped with boron, phosphorus or germanium elements.
It should be noted that, in the above-mentioned fig. 2 f) and the patterned composite substrate shown in fig. 3, the patterned composite substrate is exemplarily shown to be composed of a substrate base plate and a heterogeneous protruding microstructure located on the substrate base plate, but the preparation method provided by the embodiment of the present invention can also be applied to other patterned composite substrate products. Fig. 4 and 5 are schematic structural diagrams of two patterned composite substrates according to embodiments of the present invention, and referring to fig. 4 and 5, the patterned composite substrate specifically includes a substrate 10 and a patterned heterogeneous layer 60 located on the substrate 10, a plurality of microstructure cavities 601 are formed on a surface of the patterned heterogeneous layer 60, and the microstructure cavities 601 penetrate through the patterned heterogeneous layer 60. It will be understood by those skilled in the art that the patterned heterogeneous layer 60 with the microstructure cavities 601 and the heterogeneous raised microstructures 50 all have the same function, and can improve the growth quality of the epitaxial material, and at the same time, form a refractive index difference with the epitaxial layer, improve the light path and increase the light extraction efficiency.
Specifically, referring to fig. 4, the patterned heterogeneous layer 60 may be disposed with the same material as the first heterogeneous layer. Alternatively, referring to fig. 5, optionally, the patterned heterogeneous layer 60 includes an upper layer 61 and a lower layer 62, wherein the upper layer 61 is of the same material as the second heterogeneous layer, and the lower layer 61 is of the same material as the first heterogeneous layer.
Similarly, it is considered that the second hetero layer is doped with boron, phosphorus or germanium, so that the refractive index is changed. Therefore, in step S160, the first heterogeneous layer may be retained, so that the finally formed patterned heterogeneous layer 60 is composed of the first heterogeneous layer and the second heterogeneous layer; alternatively, to avoid the influence of the refractive index of the second heterogeneous layer, the patterning process may be appropriately adjusted to remove the second heterogeneous layer through the patterning process, and the patterned heterogeneous layer 60 finally formed is formed by patterning only the first heterogeneous layer.
Based on the same inventive concept, the embodiment of the invention also provides an LED epitaxial wafer. Fig. 6 is a schematic structural diagram of an LED epitaxial wafer according to an embodiment of the present invention, and referring to fig. 6, the LED epitaxial wafer includes the patterned composite substrate 1 provided in the above embodiment, and further includes an epitaxial layer 2 formed on the patterned composite substrate 1.
For forming epitaxial layers on the heterogeneous microstructures made of different materials, different LED epitaxial wafer growth technologies are required, and for the patterned composite substrate provided by the embodiment of the present invention, the epitaxial layer 2 on the LED epitaxial wafer may be a GaN, AlGaN epitaxial layer, or the like. The LED epitaxial wafer has the same advantageous effects as the patterned composite substrate 1 because the patterned composite substrate 1 provided in the above embodiment is used.
It is to be noted that the foregoing is only illustrative of the preferred embodiments of the present invention and the technical principles employed. It will be understood by those skilled in the art that the present invention is not limited to the particular embodiments described herein, but is capable of various obvious modifications, rearrangements, combinations and substitutions as will now become apparent to those skilled in the art without departing from the scope of the invention. Therefore, although the present invention has been described in greater detail by the above embodiments, the present invention is not limited to the above embodiments, and may include other equivalent embodiments without departing from the spirit of the present invention, and the scope of the present invention is determined by the scope of the appended claims.
Claims (11)
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