CN115911154A - Nano-array structural member, preparation method and photoelectric device - Google Patents
Nano-array structural member, preparation method and photoelectric device Download PDFInfo
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- CN115911154A CN115911154A CN202211723745.1A CN202211723745A CN115911154A CN 115911154 A CN115911154 A CN 115911154A CN 202211723745 A CN202211723745 A CN 202211723745A CN 115911154 A CN115911154 A CN 115911154A
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Abstract
The invention discloses a nano array structural member, a preparation method and a photoelectric device, wherein the nano array structural member comprises a substrate; two array layers are processed on the substrate, the two array layers are different in size, and the two array holes are overlapped and arranged on the surface layer of the substrate to form a metal auxiliary chemical etching hole array layer. The nano array structural member provided by the invention has an ideal photon absorption function, good hydrophobicity and a rough surface, can be used for manufacturing a photoelectric device with strong anti-reflection capability, can reduce the size of a semiconductor light absorber when being applied to the semiconductor photoelectric device, and is simple in manufacturing method, green, environment-friendly, low in cost, easy to integrate and manufacture and suitable for large-scale mass production.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to a nano-array structural member, a preparation method and a photoelectric device.
Background
Modern optoelectronic devices in many areas often require the use of an antireflective layer. Conventional anti-reflective coatings are expensive and not suitable for large-scale mass production.
Methods for reducing reflectance by suppressing reflection generally fall into two categories, namely enhanced transmission and enhanced absorption. To achieve enhanced absorption, conventional processes employ coatings that rely on thin film interference. The thickness of this layer should be one quarter or half wavelength light. The introduction of a multilayer structure can improve performance in view of minimum reflectivity over a wide range of spectra. However, the design and manufacturing process is complicated. Furthermore, most anti-reflective coating solutions are expensive because they require vacuum technology, which can be problematic in mass production.
Disclosure of Invention
In view of the above, the present invention has been made to provide a nanoarray structure, a method of manufacturing and a photovoltaic device that overcome or at least partially solve the above problems.
In a first aspect, there is provided a nanoarray structure comprising: a substrate;
two array layers are processed on the substrate;
the two array layers comprise a nanosphere photoetching hole array layer and a metal auxiliary chemical etching hole array layer, the nanosphere photoetching hole array layer is formed on the surface of the substrate, and the metal auxiliary chemical etching hole array layer is formed on the surface of the nanosphere photoetching hole array layer.
Optionally, the two array layers are anti-reflection layers.
In a second aspect, a method for preparing a nanoarray structure is provided, comprising:
performing nanosphere photoetching on the surface of the substrate to form a nanosphere photoetching hole array layer;
and performing metal-assisted chemical etching on the nanosphere photoetching hole array layer to form a metal-assisted chemical etching hole array layer.
Optionally, performing nanosphere lithography on the surface of the substrate includes:
forming nanospheres arranged in a single layer on the surface of the substrate;
etching the nanospheres to form pores among the etched nanospheres;
performing reactive ion beam etching on the substrate by taking the etched nanospheres as a mask to form a nanosphere photoetching hole array layer;
removing the etched nanospheres 。
Optionally, the monolayer-aligned nanospheres comprise: silica nanospheres.
Optionally, the etching the nanospheres includes:
and etching the nanospheres by adopting a plasma etching or reactive ion beam etching method to reduce the size of the nanospheres and form pores among the etched nanospheres.
Optionally, the performing metal-assisted chemical etching on the nanosphere lithography aperture array layer includes:
depositing metal nanoparticles on the surface of the nanosphere lithography hole array layer;
annealing, and obtaining metal nanospheres which are randomly distributed on the surface of the nanosphere photoetching hole array layer;
and etching in an acid solution to form a metal-assisted chemical etching hole array layer.
Optionally, the nanosphere lithography holes in the nanosphere lithography hole array layer are in a submicron scale, and the metal-assisted chemical etching holes in the metal-assisted chemical etching hole array layer are in a nanoscale.
Optionally, the substrate is made of silicon.
In a third aspect, there is provided an optoelectronic device comprising: the nanoarray structure of the first aspect.
The technical scheme provided by the embodiment of the invention at least has the following technical effects or advantages:
according to the nano array structure, the preparation method and the photoelectric device, two array layers are processed on the substrate, the nano sphere photoetching hole array layer is formed by etching the mask, namely the moth eye structure layer, and the metal auxiliary chemical etching hole formed by metal auxiliary chemical etching is superposed, so that the two array layer structures formed in the way have an ideal photon absorption function, the surface is rough, water drops fall on the surface and are not easy to form a water film, and the water drops are easier to form water balls, so that the nano array structure has good hydrophobicity, can be used for manufacturing the photoelectric device with strong anti-reflection capability, can reduce the size of a semiconductor light absorber when being applied to the semiconductor photoelectric device, and is simple in manufacturing method, green, low in cost, easy to integrate and manufacture and suitable for large-scale mass production. The invention has wide application prospect in the aspects of manufacturing solar cells and the like.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a schematic view of a nanoarray structure according to an embodiment of the invention;
FIG. 2 is a flow chart of a method of fabricating a nanoarray structure in accordance with an embodiment of the invention;
FIG. 3 is a flowchart of nanosphere lithography in an embodiment of the present invention;
FIG. 4 is a flow chart of metal assisted chemical etching in an embodiment of the present invention;
FIG. 5 is a first process diagram illustrating a manufacturing method according to an embodiment of the present invention;
FIG. 6 is a second process diagram illustrating a manufacturing method according to an embodiment of the invention;
FIG. 7 is a third process diagram illustrating a manufacturing method according to an embodiment of the present invention;
FIG. 8 is a fourth process diagram illustrating a manufacturing method according to an embodiment of the present invention;
FIG. 9 is a fifth process diagram illustrating a manufacturing method according to an embodiment of the present invention;
FIG. 10 is a sixth process schematic of a method of manufacturing in accordance with an embodiment of the present invention;
fig. 11 is a process schematic diagram seven of the manufacturing method in the embodiment of the invention.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings.
Various structural schematics according to embodiments of the present disclosure are shown in the figures. The figures are not drawn to scale, wherein certain details are exaggerated and some details may be omitted for clarity of presentation. The shapes of the various regions, layers and their relative sizes, positional relationships are shown in the drawings as examples only, and in practice deviations due to manufacturing tolerances or technical limitations are possible, and a person skilled in the art may additionally design regions/layers with different shapes, sizes, relative positions according to the actual needs.
In the context of the present disclosure, when a layer/element is referred to as being "on" another layer/element, it can be directly on the other layer/element or intervening layers/elements may be present. In addition, if a layer/element is "on" another layer/element in one orientation, then that layer/element may be "under" the other layer/element when the orientation is reversed. In the context of the present disclosure, similar or identical components may be referred to by the same or similar reference numerals.
In order to better understand the technical solutions, the technical solutions will be described in detail with reference to specific embodiments, and it should be understood that specific features in the examples and examples of the present disclosure are detailed descriptions of the technical solutions of the present application, but not limitations of the technical solutions of the present application, and technical features in the examples and examples of the present application may be combined with each other without conflict.
Referring to fig. 1, fig. 1 is a schematic view of a nano-array structure according to an embodiment of the present invention, which includes: a substrate 1; two array layers are processed on the substrate 1; the two array layers comprise a nanosphere photoetching hole array layer and a metal auxiliary chemical etching hole array layer, the nanosphere photoetching hole array layer is formed on the surface of the substrate 1, and the metal auxiliary chemical etching hole array layer is formed on the surface of the nanosphere photoetching hole array layer.
Specifically, the two array layers are anti-reflection layers. The antireflection layer plays a crucial role in the development of modern optoelectronic devices, and can be applied in many fields. For example: anti-reflective coatings are highly desirable for increasing the quantum efficiency of backlight detectors, reducing optical losses in solar cells, efficient trapping of near infrared light, and creating additional electron-hole pairs in avalanche photodiodes. The direction of light is changed through the micro-nano structure to reduce reflection, and absorption is enhanced. However, the micro-nano structure for realizing surface antireflection is diversified in form, most structures are derived from the revelation of the moth-eye structure which is found firstly in nature, but the moth-eye structure is not strong in antireflection capability.
Based on the same inventive concept, the present invention further provides a method for manufacturing a nano-array structure, please refer to fig. 2, where fig. 2 is a flowchart of a method for manufacturing a nano-array structure according to an embodiment of the present invention, including:
step S1, performing nanosphere photoetching on the surface of a substrate 1 to form a nanosphere photoetching hole array layer;
and S2, performing metal-assisted chemical etching on the nanosphere photoetching hole array layer to form a metal-assisted chemical etching hole array layer.
Specifically, step S1 is to perform nanosphere lithography on the surface of the substrate 1, please refer to fig. 3, where fig. 3 is a flowchart of nanosphere lithography according to an embodiment of the present invention, and the flowchart includes:
step S101, forming single-layer arranged nanospheres on the surface of a substrate 1;
step S102, etching the nanospheres to form pores among the etched nanospheres;
step S103, taking the etched nanospheres as a mask, and performing reactive ion beam etching on the substrate 1 to form a nanosphere photoetching hole array layer;
and step S104, removing the etched nanospheres.
Specifically, step S2 is to perform metal assisted chemical etching on the nanosphere lithography aperture array layer, please refer to fig. 4, where fig. 4 is a flow chart of metal assisted chemical etching in an embodiment of the present invention, and the flow chart includes:
step S201, depositing metal nano particles on the surface of the nanosphere photoetching hole array layer;
step S202, annealing, and obtaining metal nanospheres which are randomly distributed on the surface of the nanosphere photoetching hole array layer;
step S203, etching is carried out in an acid solution to form a metal auxiliary chemical etching hole array layer.
The process steps implemented in this embodiment are described in detail below with reference to fig. 5-11:
as shown in fig. 5, a substrate 1 is provided, the substrate 1 may be a clean transparent silicon substrate, but is not limited thereto, and before use, the silicon substrate 1 is sequentially washed in acetone, absolute ethyl alcohol and deionized water, and dried with nitrogen.
As shown in fig. 6, step S101 is performed to form a monolayer of nanospheres 3 on the surface of the substrate 1. In an alternative embodiment, the colloid layer 2 is formed on the surface of the substrate 1 by a spin coating process, and the colloid layer 2 includes a monolayer arrangement of the nanospheres 3, so as to form a monolayer arrangement of the nanospheres 3 on the surface of the substrate 1, which may be performed by a spin coating process of the prior art and will not be described in detail herein.
In an alternative embodiment, the colloid layer 2 is a single layer of silica colloid, and the nano-spheres 3 arranged in a single layer are silica nano-spheres with a very close-packed structure. The arrangement mode of the silicon dioxide nanospheres with the very compact arrangement structure is specifically that one silicon dioxide nanosphere is adjacent to 6 silicon dioxide nanospheres to form a long-range ordered hexagonal arrangement structure. Nanosphere lithography (NSL) is a simple, economical and effective lithography technique that uses highly monodisperse nanospheres as deposition or etching masks to create patterns characterized by a nanoporous pore structure, i.e., nanosphere lithography pore array layers. Compared with high-power-consumption photoetching technologies such as traditional focused ion beam photoetching and electron beam photoetching, the nanosphere photoetching has the advantages of low power consumption, small damage to the substrate 1, simple manufacturing method and the like. In view of the advantages and the development of the large-area self-assembly monodisperse nanosphere preparation technology, the nanosphere photoetching technology is widely applied to micro-nano processing. The silicon dioxide nanospheres are used as masks to prepare the nanosphere photoetching hole array layer structure through the nanosphere photoetching technology, and the method does not need photoetching through an external photoetching mask plate, so that various errors in the traditional photoetching technology are reduced, and the photoetching precision is effectively improved. The nanospheres may be formed by other methods on the surface of the substrate 1 in a monolayer arrangement, and any of the techniques available in the art can be implemented, which will not be described herein again.
As shown in fig. 7, step S102 is performed to etch the nanospheres 2, so that pores are formed between the etched nanospheres 2. Specifically, the nanospheres 2 have a certain gap before etching, and the nanospheres 2 are etched, so that the size of the nanospheres 2 per se is reduced, the gap between the nanospheres 2 is increased, and the size of the gap determines the diameter size of the nanosphere photoetching holes in the nanosphere photoetching hole array layer. In an alternative embodiment, by O 2 Plasma etching of the silica gel layer, i.e. by O 2 Plasma etching of silica nanospheres, which can be done using prior art O 2 The plasma etching process will not be described herein.
As shown in fig. 8, step S103 is executed to perform reactive ion beam etching on the substrate 1 by using the etched nanospheres 3 as a mask, so as to form a nanosphere lithography aperture array layer, which is also called a moth-eye structure. In an alternative embodiment, a nanosphere lithography aperture array layer is etched on substrate 1 using silica nanospheres as a mask by 9 minutes of reactive ion beam etching (RIE) of silicon hexafluoride. Specifically, the etching depth of the nanosphere lithography hole array layer can be determined according to specific situations, and the process can be realized by adopting the prior art process, which is not described in a repeated way.
As shown in fig. 9, step S104 is performed to remove the etched nanospheres 3. In an alternative embodiment, the surface silica nanospheres are removed by cleaning with 2% hydrofluoric acid (HF) solution for 2 minutes.
Specifically, step S2 is to perform metal assisted chemical etching on the nanosphere lithography aperture array layer, please refer to fig. 4, where fig. 4 is a flow chart of metal assisted chemical etching in an embodiment of the present invention, and the flow chart includes:
as shown in fig. 10, step S201 is performed to deposit metal nanoparticles 4 on the surface of the nanosphere lithography aperture array layer. Specifically, the metal nanoparticles 4 are randomly distributed in and out of the pores of the nanosphere lithography pores. And S202, annealing to obtain metal nanospheres distributed randomly on the surface of the nanosphere lithography hole array layer.
In an alternative embodiment, in step S201, 4nm gold particles are deposited on the surface of the nanosphere lithography hole array layer by magnetron sputtering, and the working pressure is maintained at 4.5 × 10 during the deposition process -6 The temperature is kept at room temperature of 25 ℃ by Torr, and the metal nanoparticles 4 are not limited to gold particles. And S202, annealing in air at 300 ℃ for 3 minutes to enable 4nm gold particles to be agglomerated into balls, so that gold nanospheres distributed randomly can be obtained on the surface of the nanosphere photoetching hole array layer, and the average size of the nanospheres is 6nm.
As shown in fig. 11, step S203 is performed, etching is performed in an acidic solution, and a metal-assisted chemical etching hole array layer is formed. The metal acts as a catalyst, inducing local oxidation in the acidic solution, creating pores underneath. Metal assisted chemical etching techniques can be used to create deep structures with large aspect ratios, such as nanowire or pore structures. The two array layer structures arranged vertically can provide near ideal photon absorption, thereby reducing the size of the semiconductor absorber. Specifically, the smaller the sizes of the nanosphere photoetching holes and the metal auxiliary chemical etching holes are, the better the anti-reflection degree is, but the smaller the diameter of the nanospheres in the colloid layer is, the higher the price is, and the processing cost and difficulty can also be greatly improved. Therefore, in an alternative embodiment, the nanosphere lithography holes in the nanosphere lithography hole array layer are submicron, and the metal-assisted chemical etching holes in the metal-assisted chemical etching hole array layer are nanoscale, so that the nanosphere lithography holes have a size at least one order of magnitude larger than the metal-assisted chemical etching holes. In an optional embodiment, the diameter of the silicon dioxide nanospheres is 800nm-1um before etching, the diameter of the silicon dioxide nanospheres is 500nm-800nm after etching, the gap between the silicon dioxide nanospheres after etching is 100nm-300nm, submicron nanosphere photoetching holes in the nanosphere photoetching hole array layer are formed, the traditional photoetching and expensive nanoscale electron beam photoetching processes are not needed, the processing difficulty is simple, and the cost is low. The average size of the gold nanospheres is 6nm, nanoscale metal auxiliary chemical etching holes in the metal auxiliary chemical etching hole array layer are formed, the gold nanospheres are formed by thermal annealing and distributed randomly, the nanoscale structure can be achieved without electron beam lithography, the process is simpler, the cost is lower, the process time is shorter, and the area uniformity is better.
In an alternative embodiment, the acidic solution is 10ml of 30% hydrogen peroxide (H) 2 O 2 ) The solution, 10ml of a mixed solution of 49% hydrofluoric acid (HF) solution and 100ml of deionized water solution, and a metal auxiliary chemical etching hole is etched. In the mixed solution of hydrogen peroxide and hydrofluoric acid, the corrosion rate of silicon under the metal nanospheres is far higher than that of exposed silicon. And forming metal auxiliary chemical etching holes of the porous or columnar silicon nano structure. The acidic solution may also be other acidic solutions of the prior art, which will not be described herein. On the basis of the nanosphere photoetching hole array layer with reduced reflectivity, namely the moth-eye structure, the metal auxiliary chemical etching holes formed by metal auxiliary chemical etching are formed, the surface roughness is reduced, the reflectivity is further reduced, and the novel moth-eye anti-reflection structure based on nanosphere photoetching and metal auxiliary chemical etching is realized. Specifically, the etching depth of nanosphere photoetching and metal-assisted chemical etching and the type and thickness of nanosphere colloid can be determined automatically according to needs in the actual production process so as to meet the experimental requirements under different conditions.
Based on the same inventive concept, the embodiment of the invention also provides a photoelectric device, which comprises: the invention provides a nano-array structural member. When the nano-array structural member is applied to a semiconductor photoelectric device, the size of a semiconductor light absorber can be reduced, and the manufacturing method is simple, green, environment-friendly, low in cost, easy to integrate and manufacture and suitable for large-scale mass production. The invention has wide application prospect in the aspects of manufacturing solar cells and the like.
The technical scheme provided by the embodiment of the invention at least has the following technical effects or advantages:
according to the nano array structure, the preparation method and the photoelectric device, two array holes are processed on the substrate, and a layer of metal auxiliary chemical etching holes formed by metal auxiliary chemical etching is superposed on a nano sphere photoetching hole array layer formed by mask etching, namely a moth eye structure layer.
The two array layer structures formed in the way have ideal photon absorption function, good hydrophobicity, rough surface and large stress, so that the photoelectric device with strong anti-reflection capability can be manufactured, the size of the semiconductor light absorber can be reduced when the photoelectric device is applied to a semiconductor photoelectric device, and the manufacturing method is simple, green, environment-friendly, low in cost, easy to integrate and manufacture and suitable for large-scale mass production. The preparation method provided by the invention is simple and convenient to operate, is compatible with the traditional semiconductor process, and can be used for preparing an anti-reflection structure with good anti-reflection performance and good hydrophobic performance.
In the description provided herein, numerous specific details are set forth. It is understood, however, that embodiments of the invention may be practiced without these specific details. In some instances, well-known methods, structures and techniques have not been shown in detail in order not to obscure an understanding of this description.
Similarly, it should be appreciated that in the foregoing description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding in the understanding of one or more of the various inventive aspects. However, the disclosed method should not be interpreted as reflecting an intention that: that the invention as claimed requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the claims following the detailed description are hereby expressly incorporated into this detailed description, with each claim standing on its own as a separate embodiment of this invention.
It should be noted that the above-mentioned embodiments illustrate rather than limit the invention, and that those skilled in the art will be able to design alternative embodiments without departing from the scope of the appended claims. In the claims, any reference signs placed between parentheses shall not be construed as limiting the claim. The word "comprising" does not exclude the presence of elements or steps not listed in a claim. The word "a" or "an" preceding an element does not exclude the presence of a plurality of such elements. The invention can be implemented by means of hardware comprising several distinct elements, and by means of a suitably programmed computer. In the unit claims enumerating several means, several of these means can be embodied by one and the same item of hardware. The usage of the words first, second and third, etcetera do not indicate any ordering. These words may be interpreted as names.
Claims (10)
1. A nanoarray structure, comprising: a substrate;
two array layers are processed on the substrate;
the two array layers comprise a nanosphere photoetching hole array layer and a metal auxiliary chemical etching hole array layer, wherein the nanosphere photoetching hole array layer is formed on the surface of the substrate, and the metal auxiliary chemical etching hole array layer is formed on the surface of the nanosphere photoetching hole array layer.
2. The nanoarray structure of claim 1, wherein both array layers are antireflective layers.
3. A method for preparing a nanoarray structure, comprising:
performing nanosphere photoetching on the surface of the substrate to form a nanosphere photoetching hole array layer;
and performing metal-assisted chemical etching on the nanosphere photoetching hole array layer to form a metal-assisted chemical etching hole array layer.
4. The method of claim 3, wherein performing nanosphere lithography on the substrate surface comprises:
forming nanospheres arranged in a single layer on the surface of the substrate;
etching the nanospheres to form pores among the etched nanospheres;
performing reactive ion beam etching on the substrate by taking the etched nanospheres as a mask to form a nanosphere photoetching hole array layer;
and removing the etched nanospheres.
5. The method of claim 4, wherein the monolayer arrangement of nanospheres comprises:
silica nanospheres.
6. The method of claim 4, wherein the etching the nanospheres comprises:
and etching the nanospheres by adopting a plasma etching or reactive ion beam etching method to reduce the size of the nanospheres and form pores among the etched nanospheres.
7. The method of claim 3, wherein the performing metal assisted chemical etching on the nanosphere lithography aperture array layer comprises:
depositing metal nanoparticles on the surface of the nanosphere lithography hole array layer;
annealing, and obtaining metal nanospheres which are randomly distributed on the surface of the nanosphere photoetching hole array layer;
and etching in an acid solution to form a metal-assisted chemical etching hole array layer.
8. The method of claim 7, wherein the nanosphere lithography holes in the nanosphere lithography hole array layer are in the submicron scale and the metal-assisted chemical etching holes in the metal-assisted chemical etching hole array layer are in the nanoscale.
9. The method of claim 7, wherein the substrate is silicon.
10. An optoelectronic device, comprising: a nanoarray structure as claimed in claim 1 or 2.
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