CN110911273B - Preparation method of large-area patterned graphene - Google Patents

Preparation method of large-area patterned graphene Download PDF

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CN110911273B
CN110911273B CN201911213526.7A CN201911213526A CN110911273B CN 110911273 B CN110911273 B CN 110911273B CN 201911213526 A CN201911213526 A CN 201911213526A CN 110911273 B CN110911273 B CN 110911273B
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photoresist
layer
graphene
substrate
preparation
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CN110911273A (en
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聂长斌
申钧
魏兴战
史浩飞
冯双龙
冷重钱
张之胜
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Chongqing Institute of Green and Intelligent Technology of CAS
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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
    • H01L21/04—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
    • H01L21/0405—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 semiconducting carbon, e.g. diamond, diamond-like carbon
    • H01L21/042—Changing their shape, e.g. forming recesses
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0035—Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention belongs to the technical field of two-dimensional material processing, and particularly relates to a preparation method of large-area patterned graphene and the prepared large-area patterned graphene. The method adopts a three-layer photoresist process, and comprises spin coating a first polymer supporting layer, a second soluble photoresist sacrificial layer and a third photoresist layer, developing, reactive etching and photoresist removing. According to the invention, a three-layer photoresist process is used for replacing the traditional photoresist mask etching method, so that the problem of photoresist denaturation in the graphene etching process is avoided; on the other hand, graphene is carried out under the protection of the initial polymer in the whole process of transferring to patterning, so that pollution to graphene caused by repeated gluing is avoided.

Description

Preparation method of large-area patterned graphene
Technical Field
The invention belongs to the technical field of two-dimensional material processing, and particularly relates to a preparation method of large-area patterned graphene and the prepared large-area patterned graphene.
Background
The rapid development of the large-scale industrial preparation technology of the graphene film provides material guarantee for the basic research and application development of the graphene, and the key for realizing the practical application of the graphene is to perform patterning processing on the graphene. However, due to the special material characteristics of graphene, the micro-nano patterning processing still has some technical difficulties and challenges: on one hand, the graphene is very thin, so that the high-performance photoelectric device has high requirements on the processing precision, the flatness and the spatial resolution; on the other hand, the electrical characteristics of graphene are very sensitive to the surrounding environment, and the performance of the device is affected by structural defects, residual glue pollution and the like introduced in the processing process. Therefore, how to carry out high-precision patterning processing on the graphene is a key for improving the performance of the graphene-based electronic/optoelectronic device, and has important significance.
How to prepare large-area and high-quality graphene patterns on a large scale is a key scientific and technical problem in industrialization in numerous application fields. The method for realizing the patterning of the graphene by using the photoresist as the masking layer and by using an exposure etching method is a common method for preparing large-area graphene patterns at present. However, local carbonization occurs between the photoresist and the graphene interface during the etching process, resulting in a large amount of photoresist residue on the graphene surface during the photoresist stripping process. In addition, the entire process of transferring from graphene to patterning requires repeated spin coating and removal of various polymers, which may result in generation of a large amount of impurities and defects and cause degradation of the graphene thin film. The defects limit the further application and the industrial development of the graphene to a great extent. Therefore, it is very important to find a patterning method for a graphite thin film with large area, no damage and no pollution.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing large-area patterned graphene and the prepared large-area patterned graphene, wherein the method can realize large-area and ultra-clean preparation of a target graphene pattern, and the pattern precision of the pattern can reach 1 um.
In order to achieve the purpose, the invention adopts the following scheme:
the preparation method of the large-area patterned graphene adopts a three-layer glue process, and the three-layer glue process comprises the following steps:
1) spin-coating a first polymer support layer on the surface of graphene, and transferring the graphene to the surface of a target substrate;
2) spin-coating a second soluble photoresist sacrificial layer, and drying and curing;
3) spin-coating the third layer of photoresist, drying, and performing optical exposure to obtain a photoresist pattern with a trapezoidal section structure;
4) synchronously etching the polymer supporting layer and the graphene which are not protected by the mask plate by using a reactive ion etching machine;
5) and sequentially removing the second layer of soluble photoresist, the third layer of photoresist and the polymer supporting layer by using the photoresist solution to obtain the patterned graphene.
Further, the polymer in the step 1) is organic matter such as PMMA (polymethyl methacrylate), PC (polycarbonate) and the like, and the target substrate is SiO 2 a/Si substrate or a substrate such as ROIC, and the transfer method is wet transfer.
Further, the second sacrificial layer in the step 2) is photoresist which is insoluble in acetone but is easily soluble in an alkaline developing solution, the drying temperature is 80-150 ℃, and the drying time is 30-60 minutes.
Further, the third layer of photoresist in the step 3) is positive photoresist, such as AZ3100, S1818, S1805, and the like, the drying temperature is 100 ℃, and the drying time is 10-30 minutes. Further, the trapezoidal section in the step 3) is a gradient step formed by the second sacrificial layer and the third photoresist layer.
Further, in the step 4), the used gas for etching is oxygen, and the etching power is 30-100W.
In particular, the time of etching depends on the thickness of the polymeric support layer.
Further, the degumming solution in the step 5) is developing solution and acetone.
Specifically, the exposure and development time is determined by the thickness and solubility of the two glues.
Further, the substrate needs to be dried before removing the photoresist, the drying temperature is 100-.
Further, before performing the step 2), placing the graphene/copper sheet obtained in the step 1) into an aqueous solution of hydrochloric acid/hydrogen peroxide for 10 hours, wherein the volume ratio of HCL, H2O2 and water is 2: 1: 5.
the invention has the beneficial effects that:
1) the method replaces the traditional photoresist mask etching method, the graphene is protected by the polymer supporting layer in the whole patterning process, and damage to the graphene caused by repeated spin coating, photoresist removal and other operation processes is avoided;
2) the second layer of soluble photoresist is not denatured in the etching process, the layer isolates the interaction between the photoresist and the bottom material, and the problem that the photoresist is denatured and cannot be removed is avoided;
3) the control of the cross section of the photoresist can be realized by controlling the developing time, the photoresist structure with the stepped cross section can better play the isolation role of the second layer of photoresist, and the clean preparation of the pattern of the graphene is realized.
Drawings
Fig. 1 is a process flow diagram for preparing graphite patterning.
FIG. 2 is a scanning electron microscope photograph of a cross section of the photoresist in example 1 at different development times.
Fig. 3 is an optical microscope photograph of a graphene patterned array prepared on the surface of Si/SiO2 in example 1.
Fig. 4 is a scanning electron microscope picture of the graphene pattern on the ROIC surface in example 2.
Detailed Description
The examples are given for the purpose of better illustration of the invention, but the invention is not limited to the examples. Therefore, those skilled in the art should make insubstantial modifications and adaptations to the embodiments of the present invention in light of the above teachings and remain within the scope of the invention.
Example 1 preparation of large area patterned graphene
1. Selecting 1 x 1cm of graphene growing on the surface of a copper foil to be fixed on a carrier wafer, and spin-coating 6% PMMA on the surface as a supporting layer of the graphene;
2. preparing an aqueous solution of hydrochloric acid/hydrogen peroxide, wherein the volume ratio of the aqueous solution of hydrochloric acid/hydrogen peroxide is HCL: h 2 O 2 ：H 2 O is 2: 1: 5, putting the graphene/copper sheet coated with PMMA into the solution for 10 hours;
3. after copper is completely dissolved, attaching graphene to a SiO2/Si substrate, and drying the graphene at 120 ℃;
4. spin-coating a second layer of LOR-A5 photoresist on the surface of the PMMA/graphene, and drying at 100 ℃ for 35 min; spin-coating a third layer of photoresist on the surface S1805, and then drying at 100 ℃ for 10 min;
5. exposing the substrate for 5s by an ultraviolet exposure machine under the shielding of a target mask, developing in a developing solution for 50s to obtain a target pattern with a stepped section, wherein the cross section of the photoresist is shown in figure 2, wherein a is the target pattern with the stepped section obtained by exposing 50s, b is the target pattern with the stepped section obtained by exposing 60s, and c is the target pattern with the stepped section obtained by exposing 70 s. It can be seen that the degree of dissolution of the sacrificial layer can be effectively controlled by controlling the development time. Therefore, a suitable developing time can be selected to form a trapezoidal cross section between the photoresist and the sacrificial layer (as shown in fig. 2), and finally, the effective balance between the protection degree of the graphene and the patterning precision requirement is realized.
6. And etching the substrate for 5-10min by using an oxygen plasma etching machine with the etching power of 30-100W, and simultaneously removing the exposed PMMA and graphene.
7. And drying the substrate at the temperature of 100-150 ℃ for 10-30 minutes.
8. And removing the second layer of photoresist, the third layer of photoresist and PMMA by respectively using developing solution and acetone to obtain the graphene array with the target pattern, wherein an optical microscope picture of the graphene array is shown as the attached drawing 3, wherein a is an optical microscope photo of the graphene patterned array prepared on the surface of Si/SiO2, and b is a further enlarged image of the graphene patterned array.
Example 2 preparation of large area patterned graphene
1. The selection of graphene and the dissolution process of the copper foil were the same as in example 1.
2. After copper is completely dissolved, adhering graphene to an ROIC substrate with an uneven surface, and drying the graphene at 120 ℃;
3. spin-coating a second layer of LOR-A5 photoresist on the surface of the PMMA/graphene, and drying at 170 ℃ for 30 min; spin-coating a third layer of photoresist on the surface S1805, and then drying at 100 ℃ for 10 min;
4. and exposing the substrate for 5s through an ultraviolet exposure machine under the shielding of a target mask, and developing for 40s in a developing solution to obtain a target pattern with a step-shaped section.
5. And etching the substrate for 5-10min by using an oxygen plasma etching machine with the etching power of 30-100W, and simultaneously removing the exposed PMMA and graphene.
6. And drying the etched substrate at 170 ℃ for 10min to realize the close fit between the graphene and the substrate.
7. And removing the second layer of photoresist, the third layer of photoresist and PMMA by respectively using a developing solution and acetone, namely obtaining a patterned graphene array on the surface of the ROIC, wherein an optical microscope picture of the patterned graphene array is shown in figure 4, wherein a is the patterned graphene array on the surface of the ROIC, b is a further array amplification image on the basis of a, and c is the further array amplification image on the basis of b, and the substrate and the target mask can be seen after amplification.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.

Claims (7)

1. The preparation method of the large-area patterned graphene is characterized by adopting a three-layer glue process, wherein the three-layer glue process comprises the following steps:
1) spin-coating a first polymer support layer on the surface of graphene, and transferring the polymer support layer to the surface of a target substrate, wherein the polymer is PMMA (polymethyl methacrylate) or PC (polycarbonate), and the target substrate is SiO (silicon oxide) 2 a/Si substrate or an ROIC substrate, and the transfer method is wet transfer;
2) spin-coating a second soluble photoresist sacrificial layer, and drying and curing;
3) spin-coating the third layer of photoresist, drying, exposing the substrate for 5s through an ultraviolet exposure machine, and developing in a developing solution for 40s or 50s or 60s or 70s to obtain a photoresist pattern with a trapezoidal section structure;
4) synchronously etching the polymer supporting layer and the graphene which are not protected by the mask by using a reactive ion etching machine;
5) removing the second layer of soluble photoresist, the third layer of photoresist and the polymer supporting layer in sequence by using the photoresist solution to obtain patterned graphene;
step 2) the second sacrificial layer is LOR-A5 photoresist which is insoluble in acetone but easily soluble in alkaline developing solution, the drying temperature is 80-150 ℃, and the drying time is 30-60 minutes;
and 3) the third layer of photoresist is positive photoresist, such as AZ3100, S1818, S1805 and the like, the drying temperature is 100 ℃, and the drying time is 10-30 minutes.
2. The method according to claim 1, wherein the trapezoidal section in step 3) is a gradient step formed by the second sacrificial layer and the third photoresist layer.
3. The method according to claim 1, wherein the etching gas used in step 4) is oxygen, and the etching power is 30-100W.
4. The preparation method according to claim 1, wherein the degumming solution of step 5) is a developing solution and acetone.
5. The method as claimed in claim 1, wherein the substrate is dried before the photoresist is removed, wherein the drying temperature is 100 ℃ and 150 ℃ and the drying time is 10-30 minutes.
6. The preparation method of claim 1, wherein the graphene/copper sheet obtained in step 1) is put into an aqueous solution of hydrochloric acid/hydrogen peroxide for 10 hours before step 2), and the HCl and the H are mixed 2 O 2 And water in a volume ratio of 2: 1: 5.
7. large area patterned graphene prepared by the preparation method of any one of claims 1 to 6.
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CN113412047B (en) * 2021-07-06 2022-02-22 西安工业大学 Copper-based graphene coating structure and preparation method thereof
CN114597287B (en) * 2022-03-08 2023-05-19 中国科学院重庆绿色智能技术研究院 Patterning method of room temperature infrared sensitive film

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CN106461833A (en) * 2014-06-18 2017-02-22 唯亚威通讯技术有限公司 Metal-dielectric optical filter, sensor device, and fabrication method
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