CN105045036B - Wax paper mask and preparation method thereof - Google Patents
Wax paper mask and preparation method thereof Download PDFInfo
- Publication number
- CN105045036B CN105045036B CN201510528675.8A CN201510528675A CN105045036B CN 105045036 B CN105045036 B CN 105045036B CN 201510528675 A CN201510528675 A CN 201510528675A CN 105045036 B CN105045036 B CN 105045036B
- Authority
- CN
- China
- Prior art keywords
- polymethyl methacrylate
- stencil mask
- mask
- exposure
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Electron Beam Exposure (AREA)
Abstract
The invention provides a preparation method of a wax paper maskThe method comprises the steps of exposing polymethyl methacrylate with the weight-average molecular weight of 50000-950000 to the exposure dose of 210-430 mu C/cm2The method comprises the following steps of exposing, fixing and developing to obtain the stencil mask, so that the stencil mask obtained by preparation simultaneously contains a pore-containing thin film layer for nanoparticle forming and a supporting layer containing a larger cavity during one-step forming, a cavity in the supporting layer is positioned below the pore, and the cross-sectional area of the cavity is larger than that of the pore, so that the mask and the substrate can be tightly combined, and the vignetting effect is effectively reduced when the stencil mask is used for nanoparticle forming.
Description
Technical Field
The invention belongs to the field of nanotechnology, and particularly relates to a stencil mask and a preparation method thereof.
Background
Stencil printing is a widely used technique for preparing micro-nano structures. The method generally uses a layer of open-pore film as a deposition mask, and the permeable nano particles are determined by the pore morphology of the film surface to deposit and form nano structures with the same pore morphology. The stencil printing technique has the advantages that the stencil printing technique does not have by a plurality of other micro-nano processing means: for example, no photoresist is required; the mask can be reused; can be used for processing multilayer structures and the like. It is because of these significant advantages that stencil printing has significant research prospects in both current scientific research and industrial production.
However, the stencil printing technique disclosed so far produces a halation effect due to the inherent gap between the mask and the substrate, and further affects the physical properties of the resulting nanostructure, that is, when the stencil mask and the substrate are in contact, a gap of about 10 microns always exists between the mask and the substrate due to the local unevenness of the macroscopic surface, and when nanoparticles are deposited on the substrate surface through the mask pores, the actually obtained pattern is significantly broadened due to the pinhole effect, thereby affecting the physical properties of the finally obtained nanostructure. In addition, problems such as blockage of mask pores and easy breakage of the stencil mask due to insufficient mechanical strength exist in the application process of stencil printing, so that the development of a new stencil mask is still one of important research directions in the current micro-nano processing field.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a stencil mask and a method for manufacturing the same, which can significantly reduce the halation effect when the stencil mask is applied to stencil printing.
The invention provides a preparation method of a wax paper mask, which comprises the following steps:
exposing, developing and fixing the polymethyl methacrylate-coated sample to obtain a stencil mask,
the weight average molecular weight of the polymethyl methacrylate is 50000-950000;
the exposure dose of the exposure is 210-430 mu C/cm2。
Preferably, the sample coated with polymethyl methacrylate is prepared according to the following method:
coating a polymethyl methacrylate solution on a substrate to obtain a sample coated with polymethyl methacrylate,
the solution of the polymethyl methacrylate is an organic solution of the polymethyl methacrylate,
the organic solvent is one or two of chloroform and methyl ether.
Preferably, the mass percentage of the polymethyl methacrylate in the polymethyl methacrylate solution is 1 wt% -9 wt%.
Preferably, the coating mode is spin coating.
Preferably, the rotation speed of the spin coating is 2000-6000 rpm.
Preferably, the thickness of the polymethyl methacrylate in the sample coated with the polymethyl methacrylate is 0.1-1.5 microns.
Preferably, the exposure is electron beam exposure, deep ultraviolet exposure, extreme ultraviolet exposure or X-ray exposure.
Preferably, the developing time is 30 seconds to 120 seconds.
Preferably, the fixing time is 30 seconds to 120 seconds.
The invention provides a wax paper mask which is prepared by the preparation method of the wax paper mask.
Compared with the prior art, the invention provides a preparation method of a wax paper mask, which comprises the step of exposing 210-430 mu C/cm of polymethyl methacrylate with the weight-average molecular weight of 50000-9500002Strip ofThe method comprises the following steps of exposing under a piece of the stencil mask, fixing, developing to obtain the stencil mask, forming the stencil mask at one time, wherein the mask simultaneously contains a film layer containing pores and a supporting layer containing larger cavities, the thin film layer is used for forming nano particles, the cavities in the supporting layer are located below the pores, the cross sectional areas of the cavities are larger than those of the pores, and then the mask and a substrate can be tightly combined, wherein the supporting layer containing the cavities serves as a micro-interval gap, the thickness of the supporting layer is smaller than that of the whole stencil mask and can be as low as 1 micron, and therefore, when the stencil mask is used for forming the nano particles, the halation effect can be obviously reduced.
Drawings
FIG. 1 is a schematic view of a stencil mask in various processing steps;
FIG. 2 is a back SEM image of a stencil mask prepared in example 1 of the present invention;
FIG. 3 is an SEM image of a nanopattern obtained by nanopattern printing deposition using a stencil mask prepared in example 1 of the present invention;
FIG. 4 is a SEM image of a reverse side of a stencil mask prepared in example 2 of the present invention.
Detailed Description
The invention provides a preparation method of a wax paper mask, which comprises the following steps:
exposing, developing and fixing the polymethyl methacrylate-coated sample to obtain a stencil mask,
the weight average molecular weight of the polymethyl methacrylate is 50000-950000;
the exposure dose of the exposure is 210-430 mu C/cm2。
According to the invention, a sample coated with polymethyl methacrylate is exposed, developed and fixed to obtain a stencil mask;
wherein the weight average molecular weight of the polymethyl methacrylate is preferably 50000-950000, more preferably 100000-800000, most preferably 450000-600000, and most preferably 495000-550000; the thickness of the polymethyl methacrylate in the sample coated with the polymethyl methacrylate is preferably 1-5 micrometers, and more preferably 1.2-2 micrometers.
The exposure is preferably electron beam exposure, deep ultraviolet exposure, extreme ultraviolet exposure or X-ray exposure, more preferably electron beam exposure; the exposure dose is preferably 210-430 mu C/cm2More preferably 250 to 380. mu.C/cm2Most preferably 300 to 350. mu.C/cm2(ii) a When the exposure is electron beam exposure, the acceleration voltage of the electron beam is preferably 10 KeV-20 KeV;
the inventive coated polymethyl methacrylate samples are preferably prepared according to the following method:
coating a polymethyl methacrylate (PMMA) solution on a substrate to obtain a sample coated with the PMMA; the substrate material is not particularly limited, and any substrate material known to those skilled in the art can be used to prepare a nanogap, and the substrate is preferably a silicon dioxide and silicon composite substrate; the thickness of the substrate is preferably 100nm to 1 μm, more preferably 200nm to 800nm, and most preferably 300nm to 500 nm; the solution of the polymethyl methacrylate is preferably an organic solution of the polymethyl methacrylate; the organic solvent is preferably one or two of chloroform and methyl ether; the mass percentage of the polymethyl methacrylate in the polymethyl methacrylate solution is 1 wt% -9 wt%, and more preferably 4 wt% -6 wt%.
The coating mode is not particularly limited, any known coating mode can be adopted in the field, and the method preferably adopts a spin coating method to spin-coat the polymethyl methacrylate solution on the substrate, wherein the spin coating speed is preferably 2000-6000 rpm, and more preferably 2000 rpm; the invention also comprises the step of drying the sample coated with the polymethyl methacrylate, wherein the drying temperature is preferably 170-220 ℃, more preferably 180 ℃, and the drying time is preferably 1-5 minutes, more preferably 4 minutes.
According to the present invention, in the development, the development time is preferably 30 seconds to 120 seconds, more preferably 60 seconds to 90 seconds; in the fixing, the fixing time is preferably 30 seconds to 120 seconds, and more preferably 60 seconds to 80 seconds.
In addition, the selection of the exposure region in the exposure process is not particularly limited by the present invention, and those skilled in the art can select the exposure region according to the desired pattern based on the common general knowledge in the art.
According to the invention, the stencil mask obtained after fixing can be separated from the substrate in a way of separating the stencil mask from the substrate through hydrolysis, wherein the hydrolysis is carried out in an alkaline environment, and preferably, the pH value of the hydrolysis environment is preferably 11-14; the base providing the alkaline environment is sodium hydroxide or potassium hydroxide.
According to the invention, after the hydrolysis is finished, the wax paper mask obtained by hydrolysis is washed by deionized water, and the residual sodium hydroxide solution on the surface of the mask is removed.
The invention also provides a wax paper mask prepared by the method; the stencil mask is provided with a layer containing pores for forming nano particles and a supporting layer for supporting the layer containing the pores, wherein the supporting layer contains a cavity, the cavity in the supporting layer is positioned below the pores, and the horizontal cross-sectional area of the cavity is larger than that of the pores. When the wax paper mask with the structure is used for forming nano particles, the halation effect cannot be generated; specifically, the structure of the stencil mask is schematically shown in fig. 1, and fig. 1 is a schematic structure of the stencil mask in different processing steps; specifically, in fig. 1, a is a stencil mask obtained by development and fixation, b is a stencil mask separated from a backing plate, and c is a pattern preparation diagram of stencil printing using the stencil mask. d is a sectional view of the stencil mask illustrated in a, and as can be seen from the view d, the stencil mask of the present invention includes a layer containing pores for nano-ion molding and a support layer containing a truncated cone structure below the layer containing pores, and the surface area of the upper surface of the truncated cone is larger than the cross-sectional area of the pores.
The preparation method of the wax paper mask provided by the invention comprises the step of mixing the polymethyl methacrylate with the weight-average molecular weight of 50000-950000The exposure dose of the methyl acrylate is 210-430 mu C/cm2The stencil mask is obtained by exposure, fixing and developing under the conditions of (1), so that the stencil mask obtained by preparation simultaneously contains a layer containing pores for forming nano particles and a supporting layer for supporting the layer containing the pores, the supporting layer contains cavities, the cavities in the supporting layer are positioned below the pores, the cross-sectional areas of the cavities are larger than that of the pores, the mask and the substrate can be tightly combined, the supporting layer containing the cavities serves as a micro-interval area, the thickness of the supporting layer is smaller than that of the whole stencil mask and can be as low as 1 micron, and therefore, when the stencil mask is used for forming the nano particles, a halation effect is basically not generated.
The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Mixing Si and SiO2Composite substrate of composition (wherein the lattice orientation of the Si plate is 111, SiO)2Layer thickness of 300 nm) into 1cm × 1cm pieces, respectively ultrasonically treating with acetone, absolute ethanol, and deionized water for five minutes, and blow-drying with nitrogen gas to obtain the substrate.
A chloroform solution of PMMA 671.06 (PMMA concentration of 6 wt%) with a weight average molecular weight of 950000 was spin-coated onto the substrate at 4000rmp, and baked at 180 ℃ for 4 minutes in a hot plate to obtain a polymethyl methacrylate-coated sample with a thickness of 1.2. mu.m.
The sample spin-coated with PMMA was placed in an electron beam exposure machine (Raith e _ Line) at an acceleration voltage of 15KV and at 300. mu.C/cm2Exposing at the minimum step distance of 25.6nm to obtain a pre-designed pattern, developing for 90 seconds, and fixing for one minute to obtain a stencil mask containing a substrate; the section of the PMMA photoresist pattern obtained by exposure at this time is the shape shown in the figure 1-d;
immersing the stencil mask containing the substrate in 1mol/L KOH solution, soaking for 10 minutes at 85 ℃, separating the PMMA film with the nano pores from the surface of the substrate to form an independent film, and cleaning the residual KOH solution on the surface of the film by using a large amount of deionized water to obtain the stencil mask separated from the substrate.
When the stencil mask of the tape was observed by a scanning electron microscope, the result is shown in fig. 2, and fig. 2 is an SEM image of the stencil mask prepared in example 1 of the present invention, which is back to the front, and it can be seen that there is a cavity having an elliptical bottom surface below the elliptical hole of the stencil mask.
The obtained stencil mask was applied to nanoparticle formation, and the results are shown in fig. 3, and fig. 3 is an SEM image of nanorods obtained by performing nanopaper printing deposition using the stencil mask prepared in example 1 of the present invention, and it can be seen from the figure that the nanorods prepared by using the stencil mask prepared in example of the present invention have a structure with almost no significant size expansion, much smaller than the size of the surrounding cavity.
Example 2
Mixing Si and SiO2Composite substrate of composition (wherein the lattice orientation of the Si plate is 111, SiO)2Layer thickness of 300 nm) into 1cm × 1cm pieces, respectively ultrasonically treating with acetone, absolute ethanol, and deionized water for five minutes, and blow-drying with nitrogen gas to obtain the substrate.
A chloroform solution of PMMA 671.06 (PMMA concentration of 6 wt%) with a weight average molecular weight of 950000 was spin-coated onto the substrate at 4000rmp, and baked at 180 ℃ for 4 minutes in a hot plate to obtain a polymethyl methacrylate-coated sample with a thickness of 1.2. mu.m.
The sample spin-coated with PMMA was placed in an electron beam exposure machine (Raith e _ Line) at an acceleration voltage of 15KV and at 430. mu.C/cm2Exposing at the minimum step distance of 25.6nm to obtain a pre-designed pattern, developing for 90 seconds, and fixing for one minute to obtain a stencil mask containing a substrate; the section of the PMMA photoresist pattern obtained by exposure at this time is the shape shown in the figure 1-d;
immersing the stencil mask containing the substrate in 1mol/L KOH solution, soaking for 10 minutes at 85 ℃, separating the PMMA film with the nano pores from the surface of the substrate to form an independent film, and cleaning the residual KOH solution on the surface of the film by using a large amount of deionized water to obtain the stencil mask separated from the substrate.
When the stencil mask of the tape was observed by a scanning electron microscope, the result is shown in fig. 4, and fig. 4 is an SEM image of the stencil mask prepared in example 2 of the present invention, which is back, and it can be seen that there is a cavity having a circular bottom surface below the elliptical hole of the stencil mask.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (9)
1. A method of making a stencil mask, comprising:
exposing, developing and fixing the polymethyl methacrylate-coated sample to obtain a stencil mask,
the weight average molecular weight of the polymethyl methacrylate is 50000-950000;
the exposure dose of the exposure is 300-430 mu C/cm2；
The thickness of the polymethyl methacrylate in the sample coated with the polymethyl methacrylate is 0.1-1.5 microns.
2. The method according to claim 1, wherein the sample coated with polymethyl methacrylate is prepared by the following method:
coating a polymethyl methacrylate solution on a substrate to obtain a sample coated with polymethyl methacrylate,
the solution of the polymethyl methacrylate is an organic solution of the polymethyl methacrylate,
the organic solvent of the organic solution is one or two of chloroform and methyl ether.
3. The preparation method according to claim 2, wherein the mass percentage of the polymethyl methacrylate in the polymethyl methacrylate solution is 1 wt% to 9 wt%.
4. The method according to claim 2, wherein the coating is performed by spin coating.
5. The method according to claim 4, wherein the spin coating is performed at a speed of 2000 to 6000 rpm.
6. The production method according to claim 1, wherein the exposure is electron beam exposure.
7. The production method according to claim 1, wherein the time for development is 30 seconds to 120 seconds.
8. A producing method according to claim 1, wherein said fixing time is 30 seconds to 120 seconds.
9. A stencil mask produced by the production method according to any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510528675.8A CN105045036B (en) | 2015-08-24 | 2015-08-24 | Wax paper mask and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510528675.8A CN105045036B (en) | 2015-08-24 | 2015-08-24 | Wax paper mask and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105045036A CN105045036A (en) | 2015-11-11 |
| CN105045036B true CN105045036B (en) | 2020-12-25 |
Family
ID=54451679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510528675.8A Active CN105045036B (en) | 2015-08-24 | 2015-08-24 | Wax paper mask and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105045036B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101025460A (en) * | 2006-02-22 | 2007-08-29 | 中国科学院长春光学精密机械与物理研究所 | Micro optical component positioning structure and micro channel module preparation using micro channel array |
| CN101086966A (en) * | 2006-06-07 | 2007-12-12 | 中国科学院微电子研究所 | Preparation method of nano-scale coulomb island structure |
| CN101382733A (en) * | 2008-09-27 | 2009-03-11 | 中国科学院微电子研究所 | Method for manufacturing nanoscale pattern |
| CN101813884A (en) * | 2010-03-19 | 2010-08-25 | 中国科学技术大学 | Method for preparing nano-structured matrix on surface of uneven substrate |
| CN101872120A (en) * | 2010-07-01 | 2010-10-27 | 北京大学 | Method for preparing patterned graphene |
-
2015
- 2015-08-24 CN CN201510528675.8A patent/CN105045036B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101025460A (en) * | 2006-02-22 | 2007-08-29 | 中国科学院长春光学精密机械与物理研究所 | Micro optical component positioning structure and micro channel module preparation using micro channel array |
| CN101086966A (en) * | 2006-06-07 | 2007-12-12 | 中国科学院微电子研究所 | Preparation method of nano-scale coulomb island structure |
| CN101382733A (en) * | 2008-09-27 | 2009-03-11 | 中国科学院微电子研究所 | Method for manufacturing nanoscale pattern |
| CN101813884A (en) * | 2010-03-19 | 2010-08-25 | 中国科学技术大学 | Method for preparing nano-structured matrix on surface of uneven substrate |
| CN101872120A (en) * | 2010-07-01 | 2010-10-27 | 北京大学 | Method for preparing patterned graphene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105045036A (en) | 2015-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lee et al. | Wafer‐scale Ni imprint stamps for porous alumina membranes based on interference lithography | |
| CN106809802B (en) | The preparation method of large-area metal nanometer pinpoint array in a kind of flexible substrate | |
| JP6545854B2 (en) | Method of manufacturing porous copper foil and porous copper foil using the same | |
| Zhang et al. | Wafer‐Scale Highly Ordered Anodic Aluminum Oxide by Soft Nanoimprinting Lithography for Optoelectronics Light Management | |
| KR20120021223A (en) | Substrate provided with metal nanostructure on surface thereof and method of producing the same | |
| TW201123513A (en) | Method for preparing patterned metal oxide layer or patterned metal layer by using solution type precursor or sol-gel precursor | |
| KR20030084279A (en) | A method for preparing large-area materials with well-defined nanostructure using nanoporous alumina or nano-textured aluminum | |
| KR20100026101A (en) | Stamp for superhydrophobic micro/nano hybrid surface based on anodic aluminum oxide, method of manufacturing the same, and product manufactured with the same | |
| CN101813884B (en) | Method for preparing nano-structured matrix on surface of uneven substrate | |
| CN104877164B (en) | A kind of preparation method of through hole Ordered Film | |
| CN105045036B (en) | Wax paper mask and preparation method thereof | |
| US8465655B1 (en) | Method of manufacturing polymer nanopillars by anodic aluminum oxide membrane and imprint process | |
| CN104726920A (en) | Method for preparing and transferring ultrathin perforated anode alumina template | |
| CN107999908B (en) | Manufacturing method of micro-pit array | |
| JP2023507368A (en) | Method for producing porous graphene film and film produced using the method | |
| Chu et al. | Wetting in nanopores of cylindrical anodic aluminum oxide templates: Production of gradient polymer nanorod arrays on large-area curved surfaces | |
| KR101840030B1 (en) | Fabrication method of ultra low density three-dimensional metal or ceramic thin-film structure based on photo-lithography | |
| Agheli et al. | Nanofabrication of polymer surfaces utilizing colloidal lithography and ion etching | |
| KR101189056B1 (en) | Method for preparing nano pattern without mask and with reactive ion etching | |
| CN111575653A (en) | X-ray absorption grating and manufacturing method thereof | |
| KR102203701B1 (en) | A preparation method of micro-nano composite pattern using extraction of nano particles and a preparation method of light guide plate using the same method | |
| JP6038748B2 (en) | Manufacturing method of metal parts | |
| Ming et al. | Fabrication of micro-precision sieves with high open area percentage using micro-electroforming technology | |
| Yue et al. | The fabrication of x-ray masks using proton beam writing | |
| KR102592128B1 (en) | Metal-organic framework with 3d hierarchical porous structure and method for fabricating the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |