CN117373909A - Preparation method of multilayer metal micro-nano structure - Google Patents

Preparation method of multilayer metal micro-nano structure Download PDF

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Publication number
CN117373909A
CN117373909A CN202311396847.1A CN202311396847A CN117373909A CN 117373909 A CN117373909 A CN 117373909A CN 202311396847 A CN202311396847 A CN 202311396847A CN 117373909 A CN117373909 A CN 117373909A
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photoresist layer
layer
thin
upper side
substrate
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李澧
倪明阳
隋永新
杨怀江
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Beijing Guowang Optical Technology Co ltd
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Beijing Guowang Optical Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0203—Containers; Encapsulations, e.g. encapsulation of photodiodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

The invention discloses a preparation method of a multilayer metal micro-nano structure, which is applied to the field of semiconductor preparation and comprises the following steps: providing a substrate, and preparing a thin photoresist layer which is easy to etch on the upper side of the substrate; preparing a thick photoresist layer which is not easy to etch on the upper side of the thin photoresist layer; etching and removing the thick photoresist layer and the thin photoresist layer along a partial area on the upper side of the thick photoresist layer until the substrate is exposed, so as to obtain a patterned photoresist layer; sequentially preparing a plurality of metal layers on the upper side of the exposed substrate to obtain a multi-layer metal micro-nano structure from which photoresist is to be removed; and removing the patterned photoresist layer to obtain the multilayer metal micro-nano structure. According to the invention, the thin photoresist layer which is easy to etch is prepared on the upper side of the substrate, and the thick photoresist layer which is difficult to etch is prepared on the upper side of the thin photoresist layer, so that the functionality of the photoresist layer can be ensured, and meanwhile, the thin photoresist layer which is easy to etch and is arranged on the lower side is removed when the photoresist is removed, so that the photoresist is conveniently removed, the complexity of the removal is reduced, and the preparation efficiency is improved.

Description

Preparation method of multilayer metal micro-nano structure
Technical Field
The invention relates to the field of semiconductor preparation, in particular to a preparation method of a multilayer metal micro-nano structure.
Background
The micro-nano size metal structure material can remarkably regulate and control the light field distribution of the incident light wave, has the advantages of compatibility with integrated circuit manufacturing technology, light weight, large design freedom degree, excellent regulation and control performance, contribution to mass production and the like, and the multi-layer metal micro-nano structure can realize effective light field regulation and control of the incident light wave through reasonable structural design including selected metal materials, thickness and characteristic dimensions. However, the existing preparation process is complex, the mask layer is not easy to remove after the preparation of the multi-layer metal micro-nano structure, and the cleanliness of the structure surface cannot be ensured.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a multi-layer metal micro-nano structure, which solves the problems in the prior art that a mask layer is not easy to remove after the multi-layer metal micro-nano structure is prepared, and the cleanliness of the structure surface cannot be ensured.
In order to solve the technical problems, the invention provides a preparation method of a multilayer metal micro-nano structure, which comprises the following steps:
providing a substrate, and preparing a thin photoresist layer which is easy to etch on the upper side of the substrate;
preparing a thick photoresist layer which is not easy to etch on the upper side of the thin photoresist layer;
etching and removing the thick photoresist layer and the thin photoresist layer along a partial area on the upper side of the thick photoresist layer until the substrate is exposed, so as to obtain a patterned photoresist layer;
sequentially preparing a plurality of metal layers on the upper side of the exposed substrate to obtain a multi-layer metal micro-nano structure from which photoresist is to be removed;
and removing the patterned photoresist layer to obtain the multilayer metal micro-nano structure.
Optionally, etching to remove the thick photoresist layer and the thin photoresist layer along a partial region of the upper side of the thick photoresist layer includes:
etching downwards along a partial area on the upper side of the thick photoresist layer, and removing the thick photoresist layer below the partial area until the thin photoresist layer is exposed;
and continuing to etch the thin photoresist layer along the exposed thin photoresist layer to obtain the patterned photoresist layer with the width of the etched region of the thin photoresist layer being greater than that of the etched region of the thick photoresist layer.
Optionally, continuing to etch the thin photoresist layer along the exposed thin photoresist layer to obtain the patterned photoresist layer having a width of the thin photoresist layer etching region greater than a width of the thick photoresist layer etching region, including:
and continuing to etch the thin photoresist layer along the exposed thin photoresist layer by using an inductive coupling plasma etching method so as to obtain the patterned photoresist layer with the width of the etched area of the thin photoresist layer being larger than that of the etched area of the thick photoresist layer.
Optionally, etching downwards along a partial area on the upper side of the thick photoresist layer, removing the thick photoresist layer under the partial area until the thin photoresist layer is exposed, including:
and etching downwards along a partial area on the upper side of the thick photoresist layer by utilizing an electron beam exposure and development technology, and removing the thick photoresist layer under the partial area until the thin photoresist layer is exposed.
Optionally, removing the patterned thick photoresist layer and the patterned thin photoresist layer to obtain a multi-layer metal micro-nano structure, including:
immersing the multi-layer metal micro-nano structure with photoresist to be removed in an acetone solution, and removing the patterned photoresist layer and the multi-layer metal layer on the upper side of the patterned photoresist layer to obtain the multi-layer metal micro-nano structure to be cleaned;
immersing the multi-layer metal micro-nano structure to be cleaned into ethanol for ultrasonic cleaning to obtain the multi-layer metal micro-nano structure.
Optionally, providing a substrate, and preparing a thin photoresist layer which is easy to etch on the upper side of the substrate; preparing a thick photoresist layer which is not easy to etch on the upper side of the thin photoresist layer, wherein the thick photoresist layer comprises:
providing a substrate, spin-coating a layer of thin photoresist on the upper side of the substrate, and performing pre-baking treatment to obtain the thin photoresist layer easy to etch;
and spin-coating a layer of thick photoresist on the upper side of the thin photoresist layer and performing pre-baking treatment to obtain the thick photoresist layer which is not easy to etch.
Optionally, the total thickness of the thin photoresist layer easy to etch and the thick photoresist layer difficult to etch, which are prepared on the upper side of the provided substrate, is greater than the total thickness of the prepared multi-layer metal layer.
Optionally, the thin photoresist easy to etch comprises PMMA copolymer and PMMA-MAA copolymer;
accordingly, the thick photoresist that is not easily etched includes electron beam photoresist, I-line, and 248nm and 193nm optical photoresist.
Optionally, the providing a substrate and preparing a thin photoresist layer that is easy to etch on an upper side of the substrate includes:
providing a silicon substrate or a quartz substrate, and cleaning the silicon substrate or the quartz substrate;
and preparing a thin photoresist layer which is easy to etch on the upper side of the silicon substrate or the quartz substrate.
Optionally, sequentially preparing a plurality of metal layers on the exposed upper side of the substrate to obtain a multi-layer metal micro-nano structure from which photoresist is to be removed, including:
and depositing a plurality of metal layers on the exposed upper side of the substrate by using an electron beam evaporation method or a sputtering method in sequence to obtain the multi-layer metal micro-nano structure from which the photoresist is to be removed.
It can be seen that the method for preparing the multi-layer metal micro-nano structure provided by the invention comprises the steps of providing a substrate, preparing a thin photoresist layer which is easy to etch on the upper side of the substrate, preparing a thick photoresist layer which is difficult to etch on the upper side of the thin photoresist layer, etching and removing the thick photoresist layer and the thin photoresist layer along a partial area on the upper side of the thick photoresist layer until the substrate is exposed, obtaining a patterned photoresist layer, sequentially preparing multi-layer metal layers on the upper side of the exposed substrate, obtaining the multi-layer metal micro-nano structure with the photoresist to be removed, and removing the patterned photoresist layer to obtain the multi-layer metal micro-nano structure. According to the invention, the thin photoresist layer easy to etch is prepared on the upper side of the substrate, and the thick photoresist layer difficult to etch is prepared on the upper side of the thin photoresist layer, so that the functionality of the photoresist layer can be ensured, and meanwhile, the thin photoresist layer easy to etch arranged on the lower side is removed when the photoresist is removed, so that the photoresist can be removed conveniently, the complexity of removal is reduced, and the preparation efficiency is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method for preparing a multi-layer metal micro-nano structure according to an embodiment of the present invention;
FIG. 2 is a flowchart illustrating a method for fabricating a multi-layered metal micro-nano structure according to an embodiment of the present invention;
fig. 3 to 9 are exemplary diagrams of a multi-layered metal micro-nano structure according to an embodiment of the present invention;
in fig. 3 to 9, reference numerals are explained as follows:
10-a substrate;
20-a thin photoresist layer easy to etch, and 21-a patterned thin photoresist layer;
30-a thick photoresist layer which is not easy to etch, 31-a patterned thick photoresist layer;
41-first metal layer, 42-second metal layer, 43-third metal layer.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1, fig. 1 is a flowchart of a method for preparing a multi-layered metal micro-nano structure according to an embodiment of the present invention. The method may include:
s101: providing a substrate, and preparing a thin photoresist layer which is easy to etch on the upper side of the substrate.
In this embodiment, an easily-etched thin photoresist layer is first prepared on the upper side of the substrate, so that the easily-etched thin photoresist layer is used to facilitate photoresist removal when photoresist is removed. The thickness of the thin photoresist in this embodiment may be less than 100 nanometers.
Further, in order to ensure the suitability of the provided substrate, the step of providing the substrate and preparing the thin photoresist layer which is easy to etch on the upper side of the substrate may include the following steps:
step S11: providing a silicon substrate or a quartz substrate, and cleaning the silicon substrate or the quartz substrate.
Step S12: and preparing a thin photoresist layer which is easy to etch on the upper side of the silicon substrate or the quartz substrate.
In this embodiment, the substrate is selected to be a silicon substrate or a quartz substrate, so that the multi-layer metal micro-nano structure can be prepared appropriately, and the provided silicon substrate or quartz substrate is cleaned, so that the cleanliness of the surface of the substrate can be ensured, and the yield of the subsequent preparation steps is improved.
S102: and preparing a thick photoresist layer which is not easy to etch on the upper side of the thin photoresist layer.
In this embodiment, a thick photoresist layer which is not easy to etch is prepared on the upper side of the thin photoresist layer, and a patterned photoresist layer can be obtained by etching the thick photoresist layer, so that the preparation of the multi-layer metal micro-nano structure is completed. It should be noted that, in this embodiment, the thick photoresist layer that is not easy to etch is a photoresist layer formed by selecting a material that is not easy to etch, and the thin photoresist layer that is easy to etch is a photoresist layer formed by selecting a material that is easy to etch, so as to ensure the accuracy of the dimension after patterned etching, the photoresist layer that is not easy to etch is set to be a relatively thick photoresist layer.
S103: and etching and removing the thick photoresist layer and the thin photoresist layer along a partial area on the upper side of the thick photoresist layer until the substrate is exposed, so as to obtain the patterned photoresist layer.
In this embodiment, a plurality of etching positions are selected on the upper side of the thick photoresist, corresponding positions can be selected according to the prepared multi-layer metal micro-nano structure, the photoresist layer is etched downwards along the selected positions until the substrate is exposed, and the photoresist etched at this time is used as the patterned photoresist layer. The embodiment is not limited to a specific manner of etching the photoresist layer, as long as the patterned photoresist layer can be etched. In the embodiment, the residual photoresist can be ashed by utilizing oxygen plasma, wherein the total flow of the oxygen plasma of the reaction gas is more than 50sccm, the power of a radio frequency power supply is more than 30W, the reaction temperature is normal temperature, and the residual photoresist at the bottom is etched cleanly.
Further, in order to improve the removal convenience when removing the photoresist, the etching to remove the thick photoresist layer and the thin photoresist layer along the partial region on the upper side of the thick photoresist layer may include the following steps:
step S21: and etching downwards along a partial area on the upper side of the thick photoresist layer, and removing the thick photoresist layer under the partial area until the thin photoresist layer is exposed.
Step S22: and continuing to etch the thin photoresist layer along the exposed thin photoresist layer to obtain a patterned photoresist layer with the width of the etched region of the thin photoresist layer being greater than the width of the etched region of the thick photoresist layer.
It should be noted that, in this embodiment, the width of the etching area of the thin photoresist layer that is easy to etch is greater than the width of the etching area of the thick photoresist layer that is not easy to etch, so that when the multilayer metal layer is prepared along the photoresist etching area, the multilayer metal layer is not contacted with the thin photoresist layer, and when the photoresist layer is removed, the efficiency of removing the photoresist layer is further improved.
Further, in order to ensure the efficiency of preparing the etching region of the thin photoresist layer with a width greater than that of the thick photoresist layer, the etching of the thin photoresist layer along the exposed thin photoresist layer to obtain the patterned photoresist layer with a width greater than that of the etching region of the thick photoresist layer may include:
and continuing to etch the thin photoresist layer along the exposed thin photoresist layer by using an inductive coupling plasma etching method to obtain a patterned photoresist layer with the width of the etched region of the thin photoresist layer being greater than that of the etched region of the thick photoresist layer.
In the embodiment, the thin photoresist layer which is easy to etch is etched by using an inductive coupling plasma etching method, so that the efficiency of etching the structure is ensured.
Further, in order to ensure that the etching of the thick photoresist layer can be successfully completed, the etching downwards along the partial area on the upper side of the thick photoresist layer to remove the thick photoresist layer under the partial area until the thin photoresist layer is exposed may include:
and etching downwards along a partial area on the upper side of the thick photoresist layer by utilizing an electron beam exposure and development technology, and removing the thick photoresist layer under the partial area until the thin photoresist layer is exposed.
In the embodiment, the electron beam exposure and development technology is utilized to select a plurality of positions on the upper side of the thick photoresist layer to etch downwards, so that the etching precision can be ensured, and the excellent rate of preparing the multi-layer metal micro-nano structure can be ensured.
S104: and sequentially preparing a plurality of metal layers on the upper side of the exposed substrate to obtain a multi-layer metal micro-nano structure from which the photoresist is to be removed.
In this embodiment, a plurality of metal layers are sequentially formed on the exposed upper side of the substrate, wherein the adjacent metal layers are different in material. The arrangement of the plurality of metal layers is not limited in this embodiment. In this embodiment, the materials of the adjacent metal layers between the metal layers may be different, and the thickness of each metal layer may be set according to the actual process requirement.
Further, in order to improve the efficiency of preparing the multi-layer metal layer, the preparing the multi-layer metal layer on the exposed upper side of the substrate in sequence to obtain the multi-layer metal micro-nano structure with photoresist to be removed may include:
and sequentially depositing a plurality of metal layers on the upper side of the exposed substrate by utilizing an electron beam evaporation method or a sputtering method to obtain the multi-layer metal micro-nano structure of which the photoresist is to be removed.
In the embodiment, the multi-layer metal layer is prepared by utilizing an electron beam evaporation method or a sputtering method to deposit, so that the step of preparing the multi-layer metal layer can be successfully completed.
S105: and removing the patterned photoresist layer to obtain the multilayer metal micro-nano structure.
In the embodiment, the patterned photoresist layer is removed, and the photoresist layer and the substrate can be separated conveniently by eroding the thin photoresist layer which is in contact with the substrate and is easy to etch, and the thick photoresist layer and other redundant structures on the thin photoresist layer are removed, so that the convenience in preparing the multilayer metal micro-nano structure is improved, and the preparation efficiency is improved. The characteristic dimension of the multi-layer metal micro-nano structure in the embodiment is micro-nano scale.
Further, in order to ensure the yield of the prepared multi-layer metal micro-nano structure, the removing the patterned thick photoresist layer and the patterned thin photoresist layer to obtain the multi-layer metal micro-nano structure may include the following steps:
step S31: immersing the multi-layer metal micro-nano structure with photoresist to be removed in acetone solution, removing the patterned photoresist layer and the multi-layer metal layer on the upper side of the patterned photoresist layer to obtain the multi-layer metal micro-nano structure to be cleaned.
Step S32: immersing the multi-layer metal micro-nano structure to be cleaned into ethanol for ultrasonic cleaning to obtain the multi-layer metal micro-nano structure.
In this embodiment, after immersing the multi-layer metal micro-nano structure to be photoresist removed in an acetone solution, the photoresist layer is removed by etching the thin photoresist layer which is easy to etch, and the multi-layer metal layer deposited on the upper side of the patterned photoresist layer is removed at the same time, so that only the multi-layer metal layer prepared in the etching region of the patterned photoresist layer is remained. Immersing the multi-layer metal micro-nano structure to be cleaned into ethanol for ultrasonic cleaning, so that the cleanliness of the prepared multi-layer metal micro-nano structure is ensured.
Further, in order to ensure that the photoresist layer can be prepared, providing a substrate, and preparing a thin photoresist layer which is easy to etch on the upper side of the substrate; preparing a thick photoresist layer which is not easy to etch on the upper side of the thin photoresist layer can comprise the following steps:
step S41: providing a substrate, spin-coating a thin photoresist layer on the upper side of the substrate, and performing pre-baking treatment to obtain the thin photoresist layer easy to etch.
Step S42: and spin-coating a layer of thick photoresist on the upper side of the thin photoresist layer, and performing pre-baking treatment to obtain the thick photoresist layer which is not easy to etch.
In this embodiment, photoresist layers are obtained by spin coating photoresist and performing pre-baking treatment, so that flexibility in preparing thin photoresist layers and thick photoresist layers is improved, and complexity in preparation is reduced.
Further, in order to ensure the efficiency of preparing the multi-layer metal micro-nano structure, the total thickness of the thin photoresist layer which is easy to etch and the thick photoresist layer which is difficult to etch and is prepared on the upper side of the provided substrate is larger than the total thickness of the prepared multi-layer metal layer.
In this embodiment, the total thickness of the prepared thin photoresist layer easy to etch and the thick photoresist layer difficult to etch is set to be greater than the total thickness of the prepared multi-layer metal layer, so that stability of the micro-nano structure of the multi-layer metal layer prepared in the etching area of the photoresist layer can be ensured.
Further, in order to secure the etchability of the thin photoresist layer, the thin photoresist layer may include PMMA (polymethyl methacrylate) copolymer and PMMA-MAA (methacrylic acid) copolymer;
accordingly, thick photoresists that are not readily etchable may include electron beam photoresists, I-lines, and 248nm and 193nm optical photoresists.
For better understanding of the present invention, the above-mentioned preparation method of the multi-layer metal micro-nano structure may refer to fig. 3 to 9, and fig. 3 to 9 are exemplary diagrams of the preparation of the multi-layer metal micro-nano structure according to the embodiment of the present invention. Wherein the first metal layer 41, the second metal layer 42 and the third metal layer 43 constitute a plurality of metal layers; the thick photoresist layer and the thin photoresist layer are etched and removed along a partial area of the upper side of the thick photoresist layer until the substrate is exposed, resulting in patterned thin photoresist layer 21 and patterned thick photoresist layer 31 as patterned photoresist layers. In this embodiment, the thin photoresist may be one of PMMA copolymer or PMMA-MAA copolymer.
The method for preparing the multilayer metal micro-nano structure comprises the steps of providing a substrate, preparing a thin photoresist layer which is easy to etch on the upper side of the substrate, preparing a thick photoresist layer which is difficult to etch on the upper side of the thin photoresist layer, etching and removing the thick photoresist layer and the thin photoresist layer along a partial area on the upper side of the thick photoresist layer until the substrate is exposed, obtaining a patterned photoresist layer, sequentially preparing a multilayer metal layer on the upper side of the exposed substrate, obtaining the multilayer metal micro-nano structure with the photoresist to be removed, and removing the patterned photoresist layer to obtain the multilayer metal micro-nano structure. According to the invention, the thin photoresist layer easy to etch is prepared on the upper side of the substrate, and the thick photoresist layer difficult to etch is prepared on the upper side of the thin photoresist layer, so that the functionality of the photoresist layer can be ensured, and meanwhile, the thin photoresist layer easy to etch arranged on the lower side is removed when the photoresist is removed, so that the photoresist can be removed conveniently, the complexity of removal is reduced, and the preparation efficiency is improved. In addition, the substrate is selected as the silicon substrate or the quartz substrate, so that the multi-layer metal micro-nano structure can be prepared, the provided silicon substrate or quartz substrate is cleaned, the cleanliness of the surface of the substrate can be ensured, and the excellent rate of the subsequent preparation steps is improved; the width of the etching area of the thin photoresist layer which is easy to etch is larger than that of the etching area of the thick photoresist layer which is difficult to etch, so that the multi-layer metal layer is not contacted with the thin photoresist layer when the multi-layer metal layer is prepared along the photoresist etching area, and the efficiency of removing the photoresist layer is further improved when the photoresist layer is removed; the thin photoresist layer which is easy to etch is etched by utilizing an inductive coupling plasma etching method, so that the efficiency of etching the structure is ensured; the electron beam exposure and development technology is utilized to select a plurality of positions on the upper side of the thick photoresist layer to etch downwards, so that the etching precision can be ensured, and the excellent rate of preparing the multi-layer metal micro-nano structure can be ensured; depositing and preparing a plurality of metal layers by using an electron beam evaporation method or a sputtering method, so as to ensure that the step of preparing the plurality of metal layers can be successfully completed; after immersing the multi-layer metal micro-nano structure with photoresist to be removed in an acetone solution, removing the photoresist layer by eroding the thin photoresist layer which is easy to etch, and removing the multi-layer metal layer deposited on the upper side of the imaged photoresist layer, thereby improving the removal efficiency, immersing the multi-layer metal micro-nano structure to be cleaned in ethanol for ultrasonic cleaning, and ensuring the cleanliness of the prepared multi-layer metal micro-nano structure; the photoresist layer is obtained by spin coating photoresist and pre-baking, so that the flexibility of preparing the thin photoresist layer and the thick photoresist layer is improved, and meanwhile, the preparation complexity is reduced; the total thickness of the prepared thin photoresist layer easy to etch and the thick photoresist layer difficult to etch is set to be larger than the total thickness of the prepared multi-layer metal layer, so that the stability of the micro-nano structure of the multi-layer metal layer prepared in the etching area of the photoresist layer can be ensured; the thin photoresist which is easy to etch is arranged to comprise PMMA copolymer, such as PMMA-MAA copolymer, and the thick photoresist which is difficult to etch is arranged to comprise electron beam photoresist, I line and 248nm and 193nm optical photoresist, so that the etching property of the thin photoresist layer relative to the thick photoresist layer is ensured.
In order to facilitate understanding of the present invention, the preparation method of the multi-layer metal micro-nano structure may specifically include the following steps, refer to fig. 2 specifically, and fig. 2 is a flowchart illustrating a preparation method of the multi-layer metal micro-nano structure according to an embodiment of the present invention.
Step S1: providing a silicon substrate or a quartz substrate, cleaning the silicon substrate or the quartz substrate, spin-coating a thin photoresist layer on the upper side of the cleaned silicon substrate or the quartz substrate, and performing pre-baking treatment to obtain a thin photoresist layer which is easy to etch; the thin photoresist which is easy to etch comprises PMMA (polymethyl methacrylate) copolymer and PMMA-MAA (polymethyl methacrylate with methyl methacrylate as a monomer) copolymer.
Step S2: spin coating a layer of thick photoresist on the upper side of the thin photoresist layer and performing pre-baking treatment to obtain a thick photoresist layer which is not easy to etch; thick photoresists that are not readily etchable include electron beam photoresists, I-lines, and 248nm and 193nm optical photoresists.
Step S3: and etching downwards along a partial area on the upper side of the thick photoresist layer by utilizing an electron beam exposure and development technology, and removing the thick photoresist layer under the partial area until the thin photoresist layer is exposed.
Step S4: and continuing to etch the thin photoresist layer along the exposed thin photoresist layer by using an inductive coupling plasma etching method to obtain a patterned photoresist layer with the width of the etched area of the thin photoresist layer being larger than that of the etched area of the thick photoresist layer until the substrate is exposed, thereby obtaining the patterned photoresist layer.
Step S5: sequentially depositing a plurality of metal layers on the upper side of the exposed substrate by utilizing an electron beam evaporation method or a sputtering method to obtain a multi-layer metal micro-nano structure of which the photoresist is to be removed; the total thickness of the thin photoresist layer easy to etch and the thick photoresist layer difficult to etch is greater than the total thickness of the prepared multi-layer metal layer.
Step S6: immersing the multi-layer metal micro-nano structure with photoresist to be removed in acetone solution, removing the patterned photoresist layer and the multi-layer metal layer on the upper side of the patterned photoresist layer to obtain the multi-layer metal micro-nano structure to be cleaned.
Step S7: immersing the multi-layer metal micro-nano structure to be cleaned into ethanol for ultrasonic cleaning to obtain the multi-layer metal micro-nano structure.
A preparation method of a multilayer metal micro-nano structure comprises the following steps:
(1) Providing a silicon or quartz substrate, respectively carrying out ultrasonic treatment on the silicon wafer or the quartz substrate in acetone, alcohol and deionized water for about 10 minutes, and then placing the silicon wafer into a reactor containing sulfuric acid with the content ratio of 30% concentration hydrogen peroxide of 7:3 (also called as third liquid) and heating to 125 ℃ for about 10 minutes. Then put into hot heavy water for flushing for about 2 minutes. Then placing the silicon wafer or the quartz substrate into ammonia water: 30% concentration hydrogen peroxide: heavy water is 1:1:6 (also called liquid I) and heating to 75 ℃ for about 10 minutes. Then put into hot heavy water to be washed for about 2 minutes, and finally spin-dried for standby.
Spin-coating a thin photoresist, such as PMMA or PMMA-MAA copolymer photoresist, on the cleaned substrate, pre-baking the glued sample, wherein the temperature of the pre-baking plate is 180 ℃ and the time is 2 minutes, and the thickness of the thin photoresist is less than 100nm.
(2) Spin-coating a layer of photoresist on the thin photoresist, for example, adopting electron beam lithography to prepare ZEP520A or HSQ electron beam photoresist, wherein the thickness of the spin-coated electron beam photoresist is more than 1500 nanometers, and pre-baking the glued sample, wherein the temperature of a pre-baking plate is 180 ℃ and the time is 2 minutes.
(3) According to the micro-nano structure data to be processed, the data is transmitted to an electron beam exposure device or other advanced lithography devices and is converted into a manufacturable device data format. And exposing the predesigned micro-nano structure pattern by using electron beam exposure or other advanced photoetching technology, putting the exposed sample into a developing solution, then putting into a fixing solution, matching the developing solution and the fixing solution with the adopted thick photoresist, and then taking out and putting into a sample box.
(4) And placing the sample into an inductively coupled plasma etching device, and after the vacuum environment is created by air suction, carrying out inductively coupled plasma etching on the thin photoresist at the bottom of the sample by taking the thick photoresist pattern structure as a mask, wherein the mode of etching the thin photoresist at the bottom is vertical etching.
(5) And placing the sample into an electron beam evaporation device or a sputtering device, pumping to create a vacuum environment, and sequentially depositing a plurality of layers of metal films according to actual needs, wherein the thickness of each layer of metal film is determined according to the actual needs, and the mode of depositing the plurality of layers of metal films is vertical deposition.
(6) And placing the sample into an acetone solution, performing ultrasonic treatment, accelerating the reaction of the acetone solution and the two layers of photoresist materials, dissolving and expanding the acetone solution, and removing the unnecessary photoresist and the multiple layers of metal conductive layers on the photoresist. The method for preparing the two layers of photoresist is favorable for acetone to penetrate through the multiple layers of metal conducting layers, the two layers of photoresist can be rapidly dissolved, and the surfaces of the multiple layers of metal conducting layers and the substrate layer can not be separated, so that the photoresist stripping effect is improved. And after the stripping of the multilayer metal micro-nano structure is finished, placing the sample into ethanol solution, performing ultrasonic treatment to finish the cleaning of the multilayer metal micro-nano structure, and drying by using nitrogen to obtain the prepared multilayer metal micro-nano structure.
In this specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, so that the same or similar parts between the embodiments are referred to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
Finally, it is further noted that, in this document, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The above description is made in detail of a preparation method of a multi-layer metal micro-nano structure provided by the present invention, and specific examples are applied herein to illustrate the principles and embodiments of the present invention, and the above examples are only used to help understand the method and core ideas of the present invention; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.

Claims (10)

1. The preparation method of the multilayer metal micro-nano structure is characterized by comprising the following steps of:
providing a substrate, and preparing a thin photoresist layer which is easy to etch on the upper side of the substrate;
preparing a thick photoresist layer which is not easy to etch on the upper side of the thin photoresist layer;
etching and removing the thick photoresist layer and the thin photoresist layer along a partial area on the upper side of the thick photoresist layer until the substrate is exposed, so as to obtain a patterned photoresist layer;
sequentially preparing a plurality of metal layers on the upper side of the exposed substrate to obtain a multi-layer metal micro-nano structure from which photoresist is to be removed;
and removing the patterned photoresist layer to obtain the multilayer metal micro-nano structure.
2. The method of claim 1, wherein etching the thick photoresist layer and the thin photoresist layer along a partial region of the upper side of the thick photoresist layer comprises:
etching downwards along a partial area on the upper side of the thick photoresist layer, and removing the thick photoresist layer below the partial area until the thin photoresist layer is exposed;
and continuing to etch the thin photoresist layer along the exposed thin photoresist layer to obtain the patterned photoresist layer with the width of the etched region of the thin photoresist layer being greater than that of the etched region of the thick photoresist layer.
3. The method of claim 2, further comprising continuing to etch the thin photoresist layer along the exposed thin photoresist layer to obtain the patterned photoresist layer having a width of the thin photoresist layer etched region greater than a width of the thick photoresist layer etched region, comprising:
and continuing to etch the thin photoresist layer along the exposed thin photoresist layer by using an inductive coupling plasma etching method so as to obtain the patterned photoresist layer with the width of the etched area of the thin photoresist layer being larger than that of the etched area of the thick photoresist layer.
4. The method of claim 2, wherein etching down along a partial region of the upper side of the thick photoresist layer to remove the thick photoresist layer under the partial region until the thin photoresist layer is exposed, comprises:
and etching downwards along a partial area on the upper side of the thick photoresist layer by utilizing an electron beam exposure and development technology, and removing the thick photoresist layer under the partial area until the thin photoresist layer is exposed.
5. The method of claim 1, wherein removing the patterned thick photoresist layer and the patterned thin photoresist layer to obtain the multi-layer metal micro-nano structure comprises:
immersing the multi-layer metal micro-nano structure with photoresist to be removed in an acetone solution, and removing the patterned photoresist layer and the multi-layer metal layer on the upper side of the patterned photoresist layer to obtain the multi-layer metal micro-nano structure to be cleaned;
immersing the multi-layer metal micro-nano structure to be cleaned into ethanol for ultrasonic cleaning to obtain the multi-layer metal micro-nano structure.
6. The method for preparing the multi-layer metal micro-nano structure according to claim 1, wherein a substrate is provided, and a thin photoresist layer which is easy to etch is prepared on the upper side of the substrate; preparing a thick photoresist layer which is not easy to etch on the upper side of the thin photoresist layer, wherein the thick photoresist layer comprises:
providing a substrate, spin-coating a layer of thin photoresist on the upper side of the substrate, and performing pre-baking treatment to obtain the thin photoresist layer easy to etch;
and spin-coating a layer of thick photoresist on the upper side of the thin photoresist layer and performing pre-baking treatment to obtain the thick photoresist layer which is not easy to etch.
7. The method of claim 1, wherein the total thickness of the thin photoresist layer easy to etch and the thick photoresist layer difficult to etch, which are formed on the upper side of the provided substrate, is greater than the total thickness of the metal layers.
8. The method of claim 1, wherein the thin etchable photoresist comprises a PMMA copolymer and a PMMA-MAA copolymer;
accordingly, the thick photoresist that is not easily etched includes electron beam photoresist, I-line, and 248nm and 193nm optical photoresist.
9. The method for preparing a multi-layered metal micro-nano structure according to claim 1, wherein the providing a substrate and preparing a thin photoresist layer which is easy to etch on an upper side of the substrate comprises:
providing a silicon substrate or a quartz substrate, and cleaning the silicon substrate or the quartz substrate;
and preparing a thin photoresist layer which is easy to etch on the upper side of the silicon substrate or the quartz substrate.
10. The method for preparing a multi-layered metal micro-nano structure according to claim 1, wherein sequentially preparing a plurality of metal layers on the exposed upper side of the substrate, the multi-layered metal micro-nano structure to be photoresist removed is obtained, comprising:
and depositing a plurality of metal layers on the exposed upper side of the substrate by using an electron beam evaporation method or a sputtering method in sequence to obtain the multi-layer metal micro-nano structure from which the photoresist is to be removed.
CN202311396847.1A 2023-10-26 2023-10-26 Preparation method of multilayer metal micro-nano structure Pending CN117373909A (en)

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