CN115472492A - Super-resolution photoetching structure, preparation method and pattern transfer method - Google Patents

Super-resolution photoetching structure, preparation method and pattern transfer method Download PDF

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CN115472492A
CN115472492A CN202211147820.4A CN202211147820A CN115472492A CN 115472492 A CN115472492 A CN 115472492A CN 202211147820 A CN202211147820 A CN 202211147820A CN 115472492 A CN115472492 A CN 115472492A
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layer
etching
graphene oxide
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containing anti
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罗先刚
谷雨
罗云飞
刘凯鹏
牟帅
赵泽宇
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Institute of Optics and Electronics of CAS
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Priority to PCT/CN2022/129522 priority patent/WO2024060362A1/en
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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
    • H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
    • H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
    • H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
    • H—ELECTRICITY
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    • 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
    • H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
    • H01L21/0332—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their composition, e.g. multilayer masks, materials
    • 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
    • H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
    • H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
    • H01L21/0338—Process specially adapted to improve the resolution of the mask
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    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31144—Etching the insulating layers by chemical or physical means using masks

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Abstract

The present disclosure provides a super-resolution lithography structure, a method for manufacturing the same, and a method for transferring a pattern, wherein the method for manufacturing the same includes: s1, forming a dielectric layer (2) on a substrate (1); s2, depositing a graphene oxide layer on the dielectric layer (2); s3, baking and annealing the graphene oxide layer to form a reduced graphene oxide film layer (3), wherein the reduced graphene oxide film layer (3) is used as a first hard mask layer; s4, coating a Si-containing anti-reflection coating (4) on the reduced graphene oxide thin film layer (3), wherein the Si-containing anti-reflection coating (4) is used as a second hard mask layer; and S5, sequentially depositing a metal layer (5) and coating a photosensitive layer (6) on the Si-containing anti-reflection coating (4) to obtain the super-resolution photoetching structure. The method disclosed by the invention improves the etching selection ratio between the reduced graphene oxide thin film layer and the dielectric layer, and avoids the problems of pattern collapse, deformation and the like caused by overhigh aspect ratio in the super-resolution photoetching pattern transmission.

Description

Super-resolution photoetching structure, preparation method and pattern transfer method
Technical Field
The disclosure relates to the technical field of super-resolution lithography, in particular to a super-resolution lithography structure, a preparation method and a pattern transfer method.
Background
In recent years, with the progress of miniaturization and integration of semiconductor devices, the resolution of electronic components is required to be improved. The improvement of the resolution of the device brings about the reduction of the focal depth of the photoetching pattern, and further requires the gradual thinning of the thickness of the photosensitive film layer in the actual photoetching process. During the pattern structure transfer process, the thin photosensitive film is easily consumed, and the pattern transfer cannot be effectively realized. For this reason, a common method is to add one or a group of film structures with excellent etching resistance between the photosensitive film layer and the etched layer, and to utilize the high etching selectivity of the etching-resistant film structure and the underlying material to realize conformal transfer of the pattern, the film layer is also called a hard mask layer.
The hard mask layer typically used in advanced process technologies is a Si-containing anti-reflective coating/Spin-on-carbon (SiBARC/SOC) combined film system. Due to insufficient etching selectivity of the SOC layer and the bottom etched layer, a relatively high thickness is required to achieve the pattern transfer. However, for the pattern of the super-resolution lithography, the line width becomes narrower while the height of the SOC layer remains unchanged, so that the aspect ratio of the pattern becomes high. Based on this, the SOC layer as a hard mask layer may have problems such as twisting (bowing), collapse (wiggling), and the like during the etching process.
Disclosure of Invention
Technical problem to be solved
In view of the above problems, the present disclosure provides a super-resolution lithography structure, a method for manufacturing the same, and a method for transferring a pattern, which are used to solve the technical problems that a conventional hard mask layer is easy to distort and collapse during an etching process.
(II) technical scheme
The present disclosure provides a method for manufacturing a super-resolution lithographic structure, including: s1, forming a dielectric layer on a substrate; s2, depositing a graphene oxide layer on the dielectric layer; s3, baking and annealing the graphene oxide layer to form a reduced graphene oxide film layer, wherein the reduced graphene oxide film layer is used as a first hard mask layer; s4, coating a Si-containing anti-reflection coating on the reduced graphene oxide thin film layer, wherein the Si-containing anti-reflection coating is used as a second hard mask layer; and S5, sequentially depositing a metal layer and coating a photosensitive layer on the Si-containing anti-reflection coating to obtain the super-resolution photoetching structure.
Further, S2 includes: s21, mixing graphene oxide powder with a solvent to form a graphene oxide dispersion liquid; s22, dropwise adding the graphene oxide dispersion liquid on the dielectric layer, and rotating at a low speed to uniformly spread the graphene oxide dispersion liquid; and S23, evaporating the solvent by high-speed rotation to form the graphene oxide layer.
Further, the solvent in S21 includes one of deionized water, ethanol, tetrahydrofuran, isopropanol, ethanol, N-dimethylformamide, and N-methylpyrrolidone; the concentration of the graphene oxide dispersion liquid is 1-10 mg/mL.
Further, S3 includes: baking and annealing the graphene oxide layer to N 2 Or H 2 The baking and annealing are carried out in the atmosphere, the temperature of the baking and annealing is 200-800 ℃, and the time of the baking and annealing is 0.5-5 hours.
Further, S3 includes: the thickness of the formed reduced graphene oxide film layer is 1-50 nm.
Further, the method for depositing the metal layer on the Si-containing anti-reflection coating in S5 comprises electron beam evaporation or magnetron sputtering deposition; the material of the metal layer comprises one of Ag and Al.
Further, after the step of coating the photosensitive layer by the step S5, the method further comprises the following steps: and depositing a surface metal layer on the photosensitive layer.
The present disclosure provides a method for transferring a pattern of a super-resolution lithographic structure obtained according to the above method for preparing a super-resolution lithographic structure, including: s6, exposing and developing the photosensitive layer to form a photoetching pattern structure; s7, sequentially etching the metal layer and the Si-containing anti-reflection coating, and removing the metal layer; s8, under oxygen-containing plasma gas, taking the etched Si-containing anti-reflection coating as a second hard mask layer, reducing the graphene oxide thin film layer by utilizing reactive ion etching or inductively coupled plasma etching, and removing the Si-containing anti-reflection coating; and S9, etching the dielectric layer by taking the etched reduced graphene oxide thin film layer as a first hard mask layer, and finally transferring the photoetching pattern structure to the dielectric layer or the dielectric layer and the substrate to finish pattern transfer.
Further, the method for etching the metal layer in S7 comprises ion beam etching, wherein the etching gas adopts argon gas; the method for etching the Si-containing anti-reflection coating comprises one of ion beam etching, reactive ion etching and inductively coupled plasma etching, wherein etching gas adopts SF 6 、CHF 3 And Ar.
Further, the method for etching the dielectric layer in S9 includes one of ion beam etching, reactive ion etching and inductively coupled plasma etching, and etching gas adopts SF 6 、CHF 3 And Ar.
In another aspect, the present disclosure provides a method for transferring a pattern of a super-resolution lithographic structure obtained according to the method for preparing a super-resolution lithographic structure, including: s6, exposing the photosensitive layer, removing the surface metal layer and then developing to form a photoetching pattern structure; s7, sequentially etching the metal layer and the Si-containing anti-reflection coating, and removing the metal layer; s8, under oxygen-containing plasma gas, taking the etched Si-containing anti-reflection coating as a second hard mask layer, reducing the graphene oxide thin film layer by utilizing reactive ion etching or inductively coupled plasma etching, and removing the Si-containing anti-reflection coating; and S9, etching the dielectric layer by taking the etched reduced graphene oxide thin film layer as a first hard mask layer, and finally transferring the photoetching pattern structure to the dielectric layer or the dielectric layer and the substrate to finish pattern transfer.
In another aspect, the present disclosure provides a super-resolution lithographic structure, which is prepared according to the above method for preparing a super-resolution lithographic structure.
(III) advantageous effects
According to the super-resolution photoetching structure, the preparation method and the pattern transfer method, the reduced graphene oxide film layer is used as a first hard mask layer, the Si-containing anti-reflection coating is used as a second hard mask layer, the lower layer can be etched through the alternative arrangement of the carbon layer and the silicon layer with larger etching ratio difference, and the reduced graphene oxide film layer material contains a large number of aromatic ring C atoms, has a higher energy barrier and higher impermeability to reactive gas, and has high etching resistance. The reduced graphene oxide thin film layer improves the etching selection ratio between the reduced graphene oxide thin film layer and the dielectric layer, and avoids the problems of pattern collapse, deformation and the like caused by overhigh aspect ratio in super-resolution photoetching, so that the super-resolution photoetching pattern structure can be transferred to the dielectric layer by utilizing the hard mask layer with smaller thickness.
Drawings
FIG. 1 schematically illustrates a flow chart of a method of fabricating a super-resolution lithographic structure according to an embodiment of the present disclosure;
FIG. 2 schematically depicts a flow diagram of a method of pattern transfer for a super-resolution lithographic structure according to an embodiment of the disclosure;
FIG. 3 schematically depicts a flow chart of super-resolution lithographic pattern delivery according to an embodiment of the present disclosure;
FIG. 4 is a schematic illustration of a scanning electron microscope during the transfer of a super-resolution lithographic pattern according to embodiment 1 of the present disclosure;
FIG. 5 schematically shows a cross-sectional view of a lithographic pattern structure obtained in example 1 of the present disclosure.
Detailed Description
For the purpose of promoting a better understanding of the objects, aspects and advantages of the present disclosure, reference is made to the following detailed description taken in conjunction with the accompanying drawings.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. The terms "comprises," "comprising," and the like, as used herein, specify the presence of stated features, steps, operations, and/or components, but do not preclude the presence or addition of one or more other features, steps, operations, or components.
The disclosure aims to provide a super-resolution lithography structure, a preparation method and a lithography method, aiming at the problems that the etching selection ratio between the existing SOC layer as a hard mask layer and an etched layer is low, and the phenomenon such as distortion and collapse of a graph structure is easily caused by a thicker SOC layer.
The present disclosure provides a method for manufacturing a super-resolution lithography structure, please refer to fig. 1, which includes: s1, forming a dielectric layer 2 on a substrate 1; s2, depositing a graphene oxide layer on the dielectric layer 2; s3, baking and annealing the graphene oxide layer to form a reduced graphene oxide film layer 3, wherein the reduced graphene oxide film layer 3 serves as a first hard mask layer; s4, coating a Si-containing anti-reflection coating 4 on the reduced graphene oxide thin film layer 3, wherein the Si-containing anti-reflection coating 4 serves as a second hard mask layer; and S5, sequentially depositing a metal layer 5 and coating a photosensitive layer 6 on the Si-containing anti-reflection coating 4 to obtain the super-resolution photoetching structure.
According to the method, a dielectric layer 2, a Reduced Graphene Oxide thin film layer 3 (carbon-containing hard mask layer), a Si-containing anti-reflection coating 4 (SiBARC layer), a metal layer 5 and a photosensitive layer 6 are sequentially formed on a substrate 1, an anti-etching Reduced Graphene Oxide (RGO) material is adopted to replace the existing SOC material to serve as a first hard mask layer, meanwhile, the Si-containing anti-reflection coating serves as a second hard mask layer, and etching of the next layer can be achieved through the alternate arrangement of the carbon layer and the silicon layer with large etching ratio difference. The molecular structure of the graphene contains a large number of aromatic ring C atoms, so that the graphene has a high energy barrier, high impermeability to reactive gases and high etching resistance. Thus, graphene is considered to be a good barrier candidate. However, in the actual process, it is difficult to obtain a graphene thin film with a uniform thickness on a large-sized substrate.
Graphene Oxide (GO) has high solubility due to the presence of functional groups, and is suitable for solution-based process flows. The preparation process of the GO membrane layer is simple, and the preparation process comprises the following steps: a small amount of GO dispersed liquid is taken to be soaked on a substrate, GO dispersed liquid is uniformly spread on the substrate at a lower rotating speed, and then solvent evaporation is accelerated at a higher rotating speed, so that a GO film is uniformly spread on the substrate. However, based on the ohnishi parameter, C-C bonds are more difficult to decompose under dry etch conditions than C-O and C = O bonds, with higher C/O ratios and C/H ratios corresponding to higher etch resistance. Therefore, the prepared GO thin film needs to be reduced at high temperature to reduce the proportion of O-containing functional groups, and the reduced RGO has high C content, which is important for improving the etching resistance.
Therefore, RGO as the first hard mask layer can significantly improve the etching ratio with the dielectric layer (the etched layer). The etched layer is SiO 2 For example, the results of the study showed that SOC/SiO 2 Has an etching ratio of 2,RGO/SiO 2 Is 3 to 8, wherein the etch resistance of the RGO increases with increasing annealing temperature. More importantly, the RGO material can avoid pattern collapse and deformation in super-resolution lithography. The preparation method of the SiBARC/RGO multilayer structure disclosed by the disclosure is simple, does not need harsh conditions such as high temperature and high pressure, does not need high-cost equipment, and is low in manufacturing cost.
Specifically, S1 includes: the dielectric layer 2 is prepared on the substrate 1 by thermal oxidation, electron beam evaporation, magnetron sputtering deposition, chemical vapor deposition or coating. The material of the dielectric layer 2 is SiO 2 、SiN、poly-Si、Al 2 O 3 The thickness of the dielectric layer 2 is 10-500 nm.
On the basis of the above embodiment, S2 includes: s21, mixing graphene oxide powder with a solvent to form a graphene oxide dispersion liquid; s22, dropwise adding the graphene oxide dispersion liquid on the dielectric layer 2, and rotating at a low speed to uniformly spread the graphene oxide dispersion liquid; and S23, evaporating the solvent by high-speed rotation to form the graphene oxide layer. Wherein the solvent in S21 comprises one of deionized water, ethanol, tetrahydrofuran, isopropanol, ethanol, N-dimethylformamide and N-methylpyrrolidone; the concentration of the graphene oxide dispersion liquid is 1-10 mg/mL.
The GO dispersion liquid is prepared by mixing a certain amount of GO powder prepared by a Hummers method with a solvent and carrying out ultrasonic treatment; the solvent mixed with GO is one of deionized water, ethanol, tetrahydrofuran, isopropanol, ethanol, N-dimethyl formamide and N-methyl pyrrolidone. Preferably, the concentration of the GO dispersion liquid is 1-10 mg/mL, the concentration of the GO dispersion liquid has the technical effect of uniform dispersion in the range, and a compact and uniform GO thin film can be obtained more easily. This is because too high a concentration of GO dispersion tends to cause the GO to agglomerate in the solvent.
After the GO dispersion was configured, a GO film layer was deposited using a spin-coating process. Taking the GO dispersion liquid by a pipettor, and dripping the GO dispersion liquid on the substrate for soaking for a certain time, such as 1 minute; rotating at a low rotation speed for a certain time, such as 1 minute, within a range of 500 to 700rmp, so that the GO dispersion is uniformly spread on the substrate; and then rotating at a high rotating speed for a certain time, such as 0.5 minute, wherein the rotating speed ranges from 1200rmp to 3000rmp, so as to accelerate solvent evaporation, and uniformly spreading the GO film on the substrate to form a graphene oxide layer.
On the basis of the above embodiment, S3 includes: and baking and annealing the graphene oxide layer under the atmosphere of N2 or H2 at the temperature of 200-800 ℃ for 0.5-5 hours.
The baking and annealing step is carried out at a temperature of 200 ℃ to 800 ℃ for 0.5 to 5 hours. Preferably, the baking and annealing step is carried out at 200-500 ℃, and the duration is preferably controlled to be 3-5 hours; the baking and annealing step is carried out at 500-800 ℃, the duration is preferably controlled to be 30 minutes-2 hours, and N can be selected 2 And H2, etc.
On the basis of the above embodiment, S3 includes: the thickness of the formed reduced graphene oxide thin film layer 3 is 1-50 nm.
The thickness of the reduced graphene oxide thin film layer 3 can realize the transfer of the pattern in the super-resolution lithography within the range, while the thickness of the SOC layer can be realized within the range of 100-150 nm, and the reduced graphene oxide thin film layer is favorable for avoiding the problems of pattern collapse, deformation and the like caused by overhigh aspect ratio.
On the basis of the above embodiment, the method for depositing the metal layer 5 on the Si-containing anti-reflective coating 4 in S5 includes electron beam evaporation or magnetron sputtering deposition; the material of the metal layer 5 includes one of Ag and Al.
Further, the Si-containing anti-reflective coating 4 is formed on the RGO film layer by a coating method, and the Si-containing anti-reflective coating 4 functions as a hard mask and is disposed on the RGO film layer because a thin photoresist is used in the super-resolution lithography and the thin photoresist is consumed before the RGO layer is completely etched; depositing a metal layer 5 on the Si-containing anti-reflection coating 4 by an electron beam evaporation or magnetron sputtering deposition method, wherein preferably, the material of the metal layer 5 is one of Ag and Al; the metal layer 5 is arranged because photons drive free electron coherent resonance on the surface of the metal conductor, so that Surface Plasmons (SP) are formed at a metal-medium interface, when an evanescent wave vector is the same as an SP wave vector, the evanescent wave vector and the SP wave vector can generate coherent resonance, so that the evanescent wave carrying sub-wavelength space information is enhanced, super-resolution imaging can be realized through regulation and control, and finally, a photosensitive layer 6 is formed on the metal layer 5 by using a coating method, so that a complete super-resolution photoetching structure is obtained.
On the basis of the above embodiment, the step S5 of coating the photosensitive layer 6 further includes: a surface metal layer is deposited on the photosensitive layer 6.
The super-resolution photoetching structure comprises a substrate 1, a dielectric layer 2, a reduced graphene oxide film layer 3, a Si-containing anti-reflection coating 4, a metal layer 5, a photosensitive layer 6 and a surface metal layer from bottom to top, wherein the metal layer 5, the photosensitive layer 6 and the surface metal layer form a metal/photoresist/metal resonant cavity imaging structure, and the imaging photoetching effect with higher resolution and contrast is favorably obtained.
The present disclosure further provides a method for transferring a pattern of a super-resolution lithography structure obtained according to the above method for preparing a super-resolution lithography structure, please refer to fig. 2 to 3, which includes: s6, exposing and developing the photosensitive layer 6 to form a photoetching pattern structure; s7, sequentially etching the metal layer 5 and the Si-containing anti-reflection coating 4, and removing the metal layer 5; s8, under oxygen-containing plasma gas, reducing the graphene oxide thin film layer 3 by using the etched Si-containing anti-reflection coating 4 as a second hard mask layer and by utilizing reactive ion etching or inductively coupled plasma etching, and removing the Si-containing anti-reflection coating 4; and S9, etching the dielectric layer 2 by taking the etched reduced graphene oxide film layer 3 as a first hard mask layer, and finally transferring the photoetching pattern structure to the dielectric layer 2 or the dielectric layer 2 and the substrate 1 to finish pattern transfer.
According to the method, after a dielectric layer 2, a reduced graphene oxide thin film layer 3, a Si-containing anti-reflection coating 4, a metal layer 5 and a photosensitive layer 6 are sequentially formed on a substrate 1, a photoetching pattern structure is formed in the photosensitive layer 6 at first, then the photoetching pattern structure is etched downwards layer by layer from top to bottom, the upper layer is used as an etching masking layer of the lower layer, after the etching of the lower layer is finished, the upper layer is removed, the downwards etching is continued, and the photoetching pattern structure in the photosensitive layer 6 is sequentially etched and transferred to the metal layer 5, the Si-containing anti-reflection coating 4, the reduced graphene oxide thin film layer 3 and the dielectric layer 2 (or the dielectric layer 2 and the substrate 1), so that the pattern transfer is completed. The method for etching and transferring through the multilayer structure has the advantages of simple preparation process, low manufacturing cost and high productivity.
On the basis of the above embodiment, the method for Etching the metal layer 5 in S7 includes Ion Beam Etching (IBE), and the Etching gas is argon; the method for Etching the Si-containing anti-reflection coating 4 comprises one of Ion Beam Etching (IBE), reactive Ion Etching (RIE) or inductively Coupled Plasma Etching (ICP), wherein SF is adopted as Etching gas 6 、CHF 3 And Ar.
In S7, the metal layer 5 is etched by adopting IBE, and the pattern on the photosensitive layer 6 is transferred to the metal layer 5; preferably, the etching gas is argon. Adopting IBE, RIE or ICP to etch the Si-containing anti-reflection coating 4, and transferring the photoetching pattern structure in the metal layer 5 to the SiBARC layer; the etching gas may be SF 6 、CHF 3 And Ar. And after the SiBARC layer is etched, removing the metal layer 5 by adopting a wet etching or mechanical stripping method.
In S8 containing O 2 Etching the RGO film layer by RIE or ICP, and further transferring the photoetching pattern structure in the SiBARC layer to the RGO layer. And after the RGO layer is etched, removing the SiBARC layer by adopting a wet etching method. Preferably, the etching solution is an HF solution.
On the basis of the above embodiment, the method for etching the dielectric layer 2 in S9 includes one of ion beam etching, reactive ion etching and inductively coupled plasma etching, and the etching is performedEtching gas using SF 6 、CHF 3 And Ar.
The material of the dielectric layer 2 comprises SiO 2 、SiN、poly-Si、Al 2 O 3 The etching can be carried out by RIE or ICP method, and the etching gas can be SF 6 、CHF 3 And Ar, CF may also be used 4 /O 2 、NF 3 /O 2 The combined gas of (1).
The present disclosure also provides a method for transferring a pattern of a super-resolution lithography structure obtained according to the method for preparing a super-resolution lithography structure, including:
s6, exposing the photosensitive layer 6, removing the surface metal layer, and then developing to form a photoetching pattern structure; s7, sequentially etching the metal layer 5 and the Si-containing anti-reflection coating 4, and removing the metal layer 5; s8, under oxygen-containing plasma gas, reducing the graphene oxide thin film layer 3 by using the etched Si-containing anti-reflection coating 4 as a second hard mask layer and by utilizing reactive ion etching or inductively coupled plasma etching, and removing the Si-containing anti-reflection coating 4; and S9, etching the dielectric layer 2 by taking the etched reduced graphene oxide film layer 3 as a first hard mask layer, and finally transferring the photoetching pattern structure to the dielectric layer 2 or the dielectric layer 2 and the substrate 1 to finish pattern transfer.
If the surface metal layer is prepared on the photosensitive layer 6, the developing step is performed after the surface metal layer is removed in S6, and the subsequent steps are the same as the method for transferring the super-resolution lithography structure pattern without the surface metal layer, and are not described herein again.
The present disclosure also provides a super-resolution lithography structure, which is prepared according to the preparation method of the super-resolution lithography structure.
The super-resolution photoetching structure has etching resistance, and can be applied to the manufacturing process of leading edge logic chips of super-resolution photoetching and the field of CMOS (complementary metal oxide semiconductor) process of higher-technology nodes.
The present disclosure is further illustrated by the following detailed description. The above-mentioned super-resolution lithography structure, the preparation method and the pattern transfer method are specifically described in the following embodiments. However, the following examples are only for illustrating the present disclosure, and the scope of the present disclosure is not limited thereto.
The method for preparing the super-resolution photoetching structure and the method for transferring the graph disclosed by the invention, as shown in figures 1 to 3, comprises the following steps of:
step 1: the dielectric layer 2 is prepared on the substrate 1 by thermal oxidation, electron beam evaporation, magnetron sputter deposition, chemical vapor deposition or coating. The material of the dielectric layer 2 is SiO 2 、SiN、poly-Si、Al 2 O 3 The thickness of the dielectric layer 2 is 10-500 nm; corresponds to the step S1.
Step 2: preparing GO dispersion liquid with different concentrations, and depositing a Graphene Oxide (GO) layer on the dielectric layer 2 by using methods such as a spin coating method, a spraying method, a spin coating and spraying combined method, a printing method and the like; baking the GO film layer at different temperatures to form a reduced graphene oxide film layer 3, wherein the reduced graphene oxide film layer 3 serves as a first hard mask layer; corresponds to the above steps S2 to S3.
And step 3: forming a Si-containing anti-reflection coating 4 on the reduced graphene oxide thin film layer 3 by using a coating method, wherein the Si-containing anti-reflection coating 4 is used as a second hard mask layer; corresponding to the step S4;
and 4, step 4: depositing a metal layer 5 on the Si-containing anti-reflection coating 4 by an electron beam evaporation or magnetron sputtering deposition method, preferably, the material of the metal layer 5 is one of Ag and Al;
and 5: forming a photosensitive layer 6 on the metal layer 5 by a coating method, thereby completing the preparation of the super-resolution photoetching structure; corresponding to step S5 above.
Step 6: exposing and developing the photosensitive layer 6 in the multilayer film structure to obtain a required photoetching pattern structure; corresponding to the step S6;
and 7: etching the metal layer 5 by adopting IBE (ion beam etching), and transferring the photoetching pattern structure in the photosensitive layer 6 to the metal layer 5; preferably, the etching gas is argon. Etching the Si-containing anti-reflection coating 4 by IBE, RIE or ICP to form a photoetching pattern in the metal layer 5To the Si-containing anti-reflective coating 4; the etching gas may be SF 6 、CHF 3 And Ar; removing the metal layer 5 by wet etching and mechanical stripping; corresponds to the step S7;
and 8: in the presence of O 2 Etching the reduced graphene oxide thin film layer 3 by RIE or ICP, transferring the photoetching pattern structure in the Si-containing anti-reflection coating 4 to the reduced graphene oxide thin film layer 3, and removing the silicon-containing anti-reflection coating 4; corresponding to the step S8;
and step 9: etching the bottom dielectric layer 2 or the dielectric layer 2 and the substrate 1 by utilizing IBE, RIE or ICP, and transferring the photoetching pattern structure in the reduced graphene oxide thin film layer 3 to the bottom dielectric layer 2 or the dielectric layer 2 and the substrate 1; the etching gas can adopt SF 6 、CHF 3 And Ar; corresponds to the step S9.
According to the above steps 1 to 9, 3 specific examples are provided below.
Example 1:
the implementation steps of the preparation of the super-resolution lithography structure and the pattern formation of the super-resolution lithography structure of the embodiment are as follows:
step 1: depositing a dielectric layer 2 on the substrate 1 by electron beam evaporation, the dielectric layer 2 being SiO with a thickness of 200nm 2 ；
Step 2: spin-coating a graphene oxide film at the rotation speed of 1500rmp for 30s, repeating the spin-coating for 10 times, and baking and annealing at 240 ℃ for 3 hours to form Reduced Graphene Oxide (RGO) with the thickness of 30nm; the concentration of the GO dispersion liquid is 5mg/mL, and the solvent is ethanol.
And step 3: preparing a silicon-containing anti-reflection coating 4 by adopting a spin coating process, wherein the rotating speed is 2000rmp, the spin coating time is 30s, baking is carried out for 2min on a hot plate at the temperature of 210 ℃, and the thickness of the silicon-containing anti-reflection coating 4 is 30nm;
and 4, step 4: depositing a metal layer 5 with the thickness of 40nm by using a magnetron sputtering method, wherein the metal layer 5 is an Ag layer, and the direct current power is 50W;
and 5: preparing the photosensitive layer 6 by adopting a spin coating mode, wherein the rotating speed is 4000rmp, the spin coating time is 40s, baking is carried out on a hot plate at the temperature of 100 ℃ for 3 minutes, the thickness of the obtained photoresist is 30nm, and thus the preparation of the super-resolution photoetching structure is completed.
Step 6: the photosensitive layer 6 was exposed and developed at an exposure dose of 70mJ to obtain a grating structure with a half period of 200 nm.
And 7: the photoetching pattern structure in the photosensitive layer 6 is transferred to the Ag layer by IBE etching, the selected ion beam current is 260mA, the incident angle is 10 degrees (the included angle between the normal line of the substrate and the ion beam current), and Ar gas of 14sccm is adopted for etching; removing the photosensitive layer 6;
and 8: the lithographic pattern structure was further transferred to the silicon-containing anti-reflective coating 4 by RIE etching using 20W of RF power, 20sccm of CHF 3 Etching with gas;
and step 9: preparation with 1: 1 HNO 3 : soaking the above sample in DI water for 30s, washing, and adding N 2 Blow-drying to remove the Ag layer;
step 10: the photoetching pattern structure is further transferred to the reduced graphene oxide thin film layer 3 by RIE etching, and radio frequency power of 20W and O of 20sccm are adopted 2 Etching with gas; removing the silicon-containing anti-reflection coating 4 by using an HF solution;
step 11: transferring the lithographic pattern structure further to SiO using RIE etching 2 Layer, using 20W RF power, 20sccm CHF 3 And etching by using gas.
FIG. 4 shows the grating structure in the photosensitive layer 6 of this embodiment transferred to the silicon-containing anti-reflective coating 4, the reduced graphene oxide thin film layer 3 and SiO completely and without distortion and deformation 2 Electron micrograph of layer. FIG. 5 is a sectional view of the structure of the lithographic pattern obtained in this example.
In the super-resolution lithography structure, the preparation method and the pattern transfer method provided by the embodiment, based on the RGO film layer with high etching resistance, the RGO layer with the thickness of 30nm can be used for transferring the grating pattern to SiO with the thickness of 126nm 2 Layer (as shown in fig. 5), etch ratio up to 4:1. the hard mask process of the spin coating method has low initial investment cost, uniform coating, easy control of coating thickness, and capability of controlling coating thickness compared with CVD processThe process time can be shortened.
Example 2:
the implementation steps of the preparation of the super-resolution lithography structure and the pattern formation of the super-resolution lithography structure of the embodiment are as follows:
step 1: depositing a dielectric layer 2 on a substrate 1 by electron beam evaporation, wherein the dielectric layer 2 is SiO with the thickness of 100nm 2 ；
Step 2: spin-coating a graphene oxide film at the rotation speed of 2000rmp for 30s, repeating the spin-coating for 6 times, and baking and annealing at 600 ℃ for 2 hours to form Reduced Graphene Oxide (RGO) with the thickness of 15 nm; the concentration of the GO dispersion liquid is 8mg/mL, and the solvent is N, N-dimethylformamide.
And 3, step 3: preparing a silicon-containing anti-reflection coating 4 by adopting a spin coating process, wherein the rotating speed is 4000rmp, the spin coating time is 30s, baking is carried out for 2min on a hot plate at the temperature of 210 ℃, and the thickness of the silicon-containing anti-reflection coating 4 is 20nm;
and 4, step 4: depositing a bottom metal layer 5 with the thickness of 40nm by using a magnetron sputtering method, wherein the metal layer 5 is an Ag layer, and the direct current power is 50W;
and 5: preparing the photosensitive layer 6 by adopting a spin coating mode, wherein the rotating speed is 4000rmp, the spin coating time is 40s, baking is carried out on a hot plate at the temperature of 100 ℃ for 3 minutes, the thickness of the obtained photoresist is 30nm, and thus the preparation of the super-resolution photoetching structure is completed.
Step 6: the photosensitive layer 6 was exposed and developed at an exposure dose of 80mJ, to obtain a grating structure having a half period of 120 nm.
And 7: the photoetching pattern structure in the photosensitive layer 6 is transferred to the bottom layer Ag layer by utilizing IBE etching, the selected ion beam current is 260mA, the incident angle is 10 degrees (the included angle between the normal line of the substrate and the ion beam current), and Ar gas of 14sccm is adopted for etching; removing the photosensitive layer 6;
and 8: the lithographic pattern structure was further transferred to the silicon-containing anti-reflective coating 4 by RIE etching using 20W of RF power, 20sccm of CHF 3 Etching with gas;
and step 9: preparation with 1: 1 HNO 3 : DI water solution, soaking the sample for 30s, then washing and drying by N2 to remove the Ag layer;
step 10: the photoetching pattern structure is further transferred to the reduced graphene oxide thin film layer 3 by RIE etching, and radio frequency power of 20W and O of 20sccm are adopted 2 Etching with gas; removing the silicon-containing anti-reflection coating 4 by using an HF solution;
step 11: RIE etching is used to further transfer the lithographic pattern structure to SiO 2 Layer, using 20W RF power, 20sccm CHF 3 And etching by using gas.
The embodiment is based on RGO film layer with high etching resistance, and can transfer grating pattern etching to SiO with thickness of 100nm by using RGO layer with thickness of 15nm 2 And etching the layer according to the etching ratio of 6: 1.
Example 3:
in this embodiment, a process for preparing a super-resolution lithography pattern and an etching transfer process is described, which includes the following steps:
step 1: depositing a dielectric layer 2 on the substrate 1 by electron beam evaporation, the dielectric layer 2 being SiO with a thickness of 200nm 2 ；
And 2, step: spin-coating a graphene oxide film at the rotation speed of 1500rmp for 30s, repeating the spin-coating for 15 times, and baking and annealing at 600 ℃ for 2 hours to form Reduced Graphene Oxide (RGO) with the thickness of 30nm; the concentration of the GO dispersion solution adopted is 3mg/mL, and the solvent is deionized water.
And step 3: preparing a silicon-containing anti-reflection coating 4 by adopting a spin coating process, wherein the rotating speed is 2000rmp, the spin coating time is 30s, baking is carried out for 2min on a hot plate at the temperature of 210 ℃, and the thickness of the silicon-containing anti-reflection coating 4 is 30nm;
and 4, step 4: depositing a metal layer 5 with the thickness of 40nm by using a magnetron sputtering method, wherein the metal layer 5 is an Ag layer, and the direct current power is 50W;
and 5: the photosensitive layer 6 was prepared by spin coating at 4000rmp for 40s, and baked on a 100 ℃ hotplate for 3 min to obtain a photoresist with a thickness of 30nm.
Step 6: depositing a surface metal layer with the thickness of 12nm by using a vacuum evaporation method, wherein the surface metal layer is Ag, and the deposition rate is 0.3nm/s; thus, the preparation of the resonant cavity structure of the super-resolution lithography is completed. The resonant cavity imaging structure adopting metal/photoresist/metal can play a role in further improving the resolution, and the SP imaging photoetching effect with higher resolution and contrast is further obtained because the SP of the upper metal film layer and the SP of the lower metal film layer are mutually coupled, which is beneficial to further improving the SP excitation efficiency and compressing the SP wavelength.
And 7: the photosensitive layer 6 is exposed to a dose of 200mJ 3 And removing the surface Ag and developing to obtain a through hole structure with the diameter of 65 nm.
And 8: the photoetching pattern structure in the photosensitive layer 6 is transferred to the Ag layer by IBE etching, the selected ion beam current is 260mA, the incident angle is 10 degrees (the included angle between the normal line of the substrate and the ion beam current), and Ar gas of 14sccm is adopted for etching; removing the photosensitive layer 6;
and step 9: the lithographic pattern structure was further transferred to the silicon-containing anti-reflective coating 4 by RIE etching using 20W of RF power, 20sccm of CHF 3 Etching with gas;
step 10: preparation with 1: 1 HNO 3 : soaking the above sample in DI water for 30s, washing, and adding N 2 Blow-drying to remove the Ag layer;
step 11: the photoetching pattern structure is further transferred to the reduced graphene oxide thin film layer 3 by RIE etching, and radio frequency power of 20W and O of 20sccm are adopted 2 Etching with gas; removing the silicon-containing anti-reflection coating 4 by using an HF solution;
step 12: transferring the lithographic pattern structure further to SiO using RIE etching 2 Layer, using 20W RF power, 20sccm CHF 3 And etching by using gas.
The embodiment is based on the RGO film layer with high etching resistance, can realize super-resolution lithography with the half period of 65nm, and can further transfer the pattern to the RGO film layer and SiO 2 The etching selection ratio of the dielectric layer reaches 6: 1.
The etching transfer process provided by the photoetching can successfully transfer the photoetching pattern structure to the dielectric layer or the dielectric layer and the substrate, obviously improves the etching ratio of the hard mask layer to the dielectric layer, and avoids the problems of collapse, deformation and the like of a C-containing layer during etching the dielectric layer, which influences the etching result and avoids the performance deterioration of a device for the pattern with a finer size.
The above-mentioned embodiments, objects, technical solutions and advantages of the present disclosure are further described in detail, it should be understood that the above-mentioned embodiments are only examples of the present disclosure, and should not be construed as limiting the present disclosure, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present disclosure should be included in the protection scope of the present disclosure.

Claims (12)

1. A method for preparing a super-resolution photoetching structure is characterized by comprising the following steps:
s1, forming a dielectric layer (2) on a substrate (1);
s2, depositing a graphene oxide layer on the dielectric layer (2);
s3, baking and annealing the graphene oxide layer to form a reduced graphene oxide film layer (3), wherein the reduced graphene oxide film layer (3) is used as a first hard mask layer;
s4, coating a Si-containing anti-reflection coating (4) on the reduced graphene oxide thin film layer (3), wherein the Si-containing anti-reflection coating (4) serves as a second hard mask layer;
and S5, sequentially depositing a metal layer (5) and coating a photosensitive layer (6) on the Si-containing anti-reflection coating (4) to obtain the super-resolution photoetching structure.
2. The method for preparing a super-resolution lithographic structure as in claim 1, wherein said S2 comprises:
s21, mixing graphene oxide powder with a solvent to form a graphene oxide dispersion liquid;
s22, dropwise adding the graphene oxide dispersion liquid on the dielectric layer (2), and rotating at a low speed to uniformly spread the graphene oxide dispersion liquid;
and S23, evaporating the solvent by high-speed rotation to form the graphene oxide layer.
3. The method for preparing a super-resolution lithographic structure as claimed in claim 2, wherein the solvent in S21 comprises one of deionized water, ethanol, tetrahydrofuran, isopropanol, ethanol, N-dimethylformamide, and N-methylpyrrolidone;
the concentration of the graphene oxide dispersion liquid is 1-10 mg/mL.
4. The method for preparing a super-resolution lithographic structure according to claim 1, wherein the step S3 comprises:
and baking and annealing the graphene oxide layer under the atmosphere of N2 or H2 at the temperature of 200-800 ℃ for 0.5-5 hours.
5. The method for fabricating a super-resolution lithographic structure as claimed in claim 4, wherein said S3 further comprises:
the thickness of the formed reduced graphene oxide film layer (3) is 1-50 nm.
6. The method for preparing a super-resolution lithographic structure according to claim 1, wherein the method for depositing the metal layer (5) on the Si-containing anti-reflective coating (4) in S5 comprises electron beam evaporation or magnetron sputtering deposition;
the material of the metal layer (5) comprises one of Ag and Al.
7. The method for preparing a super-resolution lithographic structure as claimed in claim 1, wherein said step S5 further comprises, after coating said photosensitive layer (6):
and depositing a surface metal layer on the photosensitive layer (6).
8. A method for transferring patterns of a super-resolution lithography structure obtained by the method for preparing a super-resolution lithography structure according to any one of claims 1 to 6, comprising:
s6, exposing and developing the photosensitive layer (6) to form a photoetching pattern structure;
s7, sequentially etching the metal layer (5) and the Si-containing anti-reflection coating (4), and removing the metal layer (5);
s8, under oxygen-containing plasma gas, etching the reduced graphene oxide thin film layer (3) by using the etched Si-containing anti-reflection coating (4) as a second hard mask layer and by using reactive ion etching or inductively coupled plasma, and removing the Si-containing anti-reflection coating (4);
and S9, etching the dielectric layer (2) by taking the etched reduced graphene oxide thin film layer (3) as a first hard mask layer, and finally transferring the photoetching pattern structure to the dielectric layer (2) or the dielectric layer (2) and the substrate (1) to finish pattern transfer.
9. The method of pattern transfer according to claim 8, wherein the method of etching the metal layer (5) in S7 comprises ion beam etching, and the etching gas is argon;
the method for etching the Si-containing anti-reflection coating (4) comprises one of ion beam etching, reactive ion etching and inductively coupled plasma etching, and SF is adopted as etching gas 6 、CHF 3 And Ar.
10. The method of claim 8, wherein the etching of the dielectric layer (2) in S9 comprises one of ion beam etching, reactive ion etching and inductively coupled plasma etching, and the etching gas is SF 6 、CHF 3 And Ar.
11. A method for transferring patterns of the super-resolution lithography structure obtained by the method for preparing the super-resolution lithography structure according to claim 7, comprising:
s6, exposing the photosensitive layer (6), removing the surface metal layer, and then developing to form a photoetching pattern structure;
s7, sequentially etching the metal layer (5) and the Si-containing anti-reflection coating (4), and removing the metal layer (5);
s8, under oxygen-containing plasma gas, etching the reduced graphene oxide thin film layer (3) by using the etched Si-containing anti-reflection coating (4) as a second hard mask layer and by using reactive ion etching or inductively coupled plasma, and removing the Si-containing anti-reflection coating (4);
and S9, etching the dielectric layer (2) by taking the etched reduced graphene oxide thin film layer (3) as a first hard mask layer, and finally transmitting the photoetching pattern structure to the dielectric layer (2) or the dielectric layer (2) and the substrate (1) to finish pattern transmission.
12. A super-resolution lithographic structure, characterized in that it is prepared according to the method of any one of claims 1 to 7.
CN202211147820.4A 2022-09-20 2022-09-20 Super-resolution photoetching structure, preparation method and pattern transfer method Pending CN115472492A (en)

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