CN113946006B - Large-area micro-nano grating and preparation method and application thereof - Google Patents
Large-area micro-nano grating and preparation method and application thereof Download PDFInfo
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- CN113946006B CN113946006B CN202111176238.6A CN202111176238A CN113946006B CN 113946006 B CN113946006 B CN 113946006B CN 202111176238 A CN202111176238 A CN 202111176238A CN 113946006 B CN113946006 B CN 113946006B
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- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 230000003287 optical effect Effects 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/18—Diffraction gratings
- G02B5/1847—Manufacturing methods
- G02B5/1857—Manufacturing methods using exposure or etching means, e.g. holography, photolithography, exposure to electron or ion beams
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
- G02B27/01—Head-up displays
- G02B27/017—Head mounted
- G02B27/0172—Head mounted characterised by optical features
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/18—Diffraction gratings
- G02B5/1809—Diffraction gratings with pitch less than or comparable to the wavelength
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
- G02B27/01—Head-up displays
- G02B27/017—Head mounted
- G02B2027/0178—Eyeglass type
Abstract
The invention relates to a large-area micro-nano grating and a preparation method and application thereof. The preparation method comprises the following steps: forming a metal layer on a substrate; forming a resist layer on the substrate and the metal layer, wherein the resist layer covers the metal layer; spot-coating conductive metal slurry on the surface of the corrosion-resistant layer to serve as a focusing point; the focusing points are arranged at intervals on the periphery of a preset exposure area of the resist layer; the sizes of a sub-field and a main field of the electron beam equipment are adjusted to be integral multiples of the period of the large-area micro-nano grating, and a field splicing line is enabled to fall in an exposure area; exposing and developing the resist layer to obtain a preset structure, and exposing the resist layer in electron beam equipment; ion etching is carried out on the metal layer by taking the exposed and developed resist layer as a first mask; and removing the corrosion-resistant layer, and carrying out ion etching on the substrate by taking the ion-etched metal layer as a second mask. The area of the grating obtained by the preparation method can reach the level of square centimeter, and the accuracy of the grating can reach the nanometer size.
Description
Technical Field
The invention relates to the technical field of grating preparation, in particular to a large-area micro-nano grating and a preparation method and application thereof.
Background
Gratings are commonly used optical elements, and with the increasing popularity of smart glasses, such as Virtual Reality (VR) and Augmented Reality (AR) Augmented Reality, the use of large area micro-nano gratings is becoming more common. Traditional large-area gratings are processed by a mechanical machine tool generally, and the minimum size is in the micrometer scale. In order to obtain a nano-grating of smaller size, electron beam exposure is typically used to achieve the preparation of the nano-scale grating. However, as the area of the grating increases, the grating prepared by the traditional electron beam exposure has a series of problems such as obvious splicing field error, poor focusing, deformation of patterns and the like, and poor width uniformity of grating ridges and grating grooves.
Disclosure of Invention
Based on this, it is necessary to provide a large-area micro-nano grating which has a large area and high uniformity of grating ridge and grating groove width and is suitable for mass production, and a preparation method and application thereof.
In one aspect of the invention, a method for preparing a large-area micro-nano grating is provided, which comprises the following steps:
forming a metal layer on a substrate; the thickness of the metal layer is 30 nm-80 nm;
forming a resist layer on the substrate and the metal layer, wherein the resist layer covers the metal layer;
spot-coating conductive metal slurry on the surface of the corrosion-resistant layer to serve as a focusing point; the focusing points are arranged at intervals on the periphery of a preset exposure area on the surface of the resist layer;
the sizes of a sub-field and a main field of the electron beam equipment are adjusted to be integral multiples of a preset period of the large-area micro-nano grating to be prepared, and a field splicing line falls in the preset exposure area;
exposing and developing the resist layer to obtain a preset structure, wherein the exposure is performed by the electron beam equipment;
ion etching is carried out on the metal layer by taking the exposed and developed anti-corrosion layer as a first mask;
and removing the corrosion-resistant layer, and carrying out ion etching on the substrate by taking the metal layer subjected to ion etching as a second mask.
In some embodiments, the interval between adjacent focusing points is 1 mm-10 mm.
In some of these embodiments, the resist layer has a thickness of 200nm to 300nm.
In some of these embodiments, the material of the metal layer is selected from at least one of chromium, aluminum, and titanium.
In some of these embodiments, the subfield size is 1 to 73 times the preset period;
in some of these embodiments, the main field size is 1 to 1470 times the preset period.
In some of these embodiments, in the step of exposing and developing the resist layer, the exposure dose is 1C/m 2 ～10C/m 2 。
In some of these embodiments, in the step of ion etching the metal layer using the exposed and developed resist layer as a first mask, the etching gas includes O 2 And Cl 2 The O is 2 The flow rate of the solution is 10sccm to 20sccm, the Cl 2 The flow rate of the etching solution is 30 sccm-80 sccm, and the etching power is 100W-1200W.
In some of these embodiments, in the step of ion etching the substrate with the ion etched metal layer as the second mask, the etching gas includes O 2 And CHF 3 The O is 2 The flow rate of the CHF is 3sccm to 20sccm 3 The flow rate of the etching solution is 30 sccm-80 sccm, and the etching power is 100W-1200W.
The invention also provides a large-area micro-nano grating, which is prepared by the preparation method of the large-area micro-nano grating.
On the other hand, the invention also provides application of the large-area micro-nano grating in preparing intelligent glasses or optical devices.
According to the preparation method of the large-area micro-nano grating, the sizes of the main field and the sub-field of the electron beam equipment are adjusted to be integral multiples of the grating period, and the spliced lines fall in the exposure area, so that the problems of grating ridge offset, discontinuity and the like caused by splicing field errors when the large-area grating is prepared can be reduced; by arranging the conductive metal paste at uniform intervals on the periphery of the exposure area as a focusing point, focusing is carried out on the focusing point, the problem of poor focus of large-area exposure can be solved, the precision of a photoetching pattern is improved, the area of the prepared large-area micro-nano grating can reach the level of square centimeter, and meanwhile, the precision of the line width of the grating can reach the nano size.
Drawings
FIG. 1 is a process flow diagram of a method for fabricating a large area micro-nano grating according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a metal layer and a substrate obtained in step S110 in a process flow chart of the method for manufacturing a large-area micro-nano grating shown in FIG. 1;
FIG. 3 is a schematic diagram of a resist layer, a metal layer and a substrate obtained in step S120 in a process flow chart of the method for manufacturing a large-area micro-nano grating shown in FIG. 1;
FIG. 4 is a schematic diagram of the resist layer and the focus point obtained in step S130 in the process flow chart of the method for manufacturing a large-area micro-nano grating shown in FIG. 1;
FIG. 5 is a schematic diagram of a resist layer, a metal layer and a substrate obtained in step S150 in a process flow chart of the method for manufacturing a large-area micro-nano grating shown in FIG. 1;
FIG. 6 is a schematic diagram of the resist layer, the metal layer and the substrate obtained in step S160 in the process flow chart of the method for manufacturing a large-area micro-nano grating shown in FIG. 1;
FIG. 7 is a schematic diagram of a metal layer and a substrate obtained by removing the resist layer in step S170 in the process flow chart of the method for manufacturing a large-area micro-nano grating shown in FIG. 1;
FIG. 8 is a schematic diagram of a metal layer and a substrate obtained by ion etching in step S170 in a process flow chart of the method for manufacturing a large-area micro-nano grating shown in FIG. 1;
FIG. 9 is a schematic diagram of a substrate obtained by removing a metal layer after step S170 in the process flow chart of the method for manufacturing a large-area micro-nano grating shown in FIG. 1;
FIG. 10 is a Scanning Electron Microscope (SEM) photograph of a large-area micro-nano-grating prepared by the method of preparing a large-area micro-nano-grating of example 1; the scale bar is 2 mu m;
FIG. 11 is a Scanning Electron Microscope (SEM) photograph of a large-area micro-nano-grating prepared by the method of preparing a large-area micro-nano-grating of comparative example 2; the scale bar is 200nm.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1, an embodiment of the present invention provides a method for preparing a large-area micro-nano grating, which includes steps S110 to S170.
Step S110: a metal layer is formed on a substrate, and the thickness of the metal layer is 30 nm-80 nm.
Fig. 2 is a schematic diagram of the metal layer 220 and the substrate 210 obtained in step S110.
The metal layer formed on the substrate may promote conductivity to collect electrons and may act as an etch mask for the substrate. In some of these embodiments, the material of the metal layer is selected from at least one of chromium, aluminum, and titanium.
Too small thickness of the metal layer can cause poor conductivity, poor etching effect and large error of the spliced position; the metal layer is too thick, so that the metal layer is not easy to be etched through in the subsequent ion etching, and a resist layer with larger thickness is needed to be used as a mask. Specifically, the thickness of the metal layer is 30nm, 40nm, 50nm, 60nm, 70nm or 80nm.
In some embodiments, the metal is evaporated using an electron beam evaporation apparatus to form a metal layer on the substrate.
In some of these embodiments, before step S110, further includes: and cleaning the substrate.
Specifically, the step of cleaning the substrate includes: the substrate is cleaned with the SC1 cleaning solution and then cleaned with the SC2 cleaning solution. Wherein the SC1 cleaning solution comprises NH 4 OH、H 2 O 2 And water. NH in SC1 cleaning solution 4 OH、H 2 O 2 And the volume ratio of water is 1:1: (5-10). The SC2 cleaning solution comprises HCl, H 2 O 2 And water. HCl, H in SC2 cleaning solution 2 O 2 And the volume ratio of water is 1:1: (5-10).
The SC1 cleaning solution can remove the particulate matters on the substrate, and the SC2 cleaning solution can remove the heavy metals on the substrate so as to prevent pollution to the subsequent preparation of the grating.
In this embodiment, the substrate is a quartz substrate, and it is understood that in other embodiments, the substrate may be selected according to the application of the large-area micro-nano grating to be manufactured.
After the step of cleaning the substrate, further comprising: and baking the substrate.
Specifically, in the step of baking the substrate, the baking temperature is 120-180 ℃, and the baking time is 1-30 min.
Step S120: a resist layer is formed over the substrate and the metal layer, the resist layer covering the metal layer.
Fig. 3 is a schematic diagram of the resist layer 230, the metal layer 220 and the substrate 210 obtained in step S120.
In some of these embodiments, the resist layer is prepared from an electron beam resist. Specifically, the electron beam resist is selected from one of polymethyl methacrylate (PMMA), ZEP520 and AR-P6200. Wherein ZEP520 is an electron beam resist manufactured by zeon corporation, and AR-P6200 is an electron beam resist manufactured by All resin corporation, germany. It is to be understood that the electron beam resist is not limited to the above-described electron beam resist, but may be an electron beam resist commonly used in the art.
Specifically, a resist layer is formed on a substrate by spin coating.
In some of these embodiments, the resist layer has a thickness of 200nm to 300nm. Specifically, the resist layer has a thickness of 200nm, 210nm, 220nm, 230nm, 240nm, 250nm, 260nm, 270nm, 280nm, 290nm or 300nm.
In some of these embodiments, the e-beam resist is AR-P6200, and the thickness ratio of the resist layer to the metal layer is (4-8): 1. preferably, the electron beam resist is AR-P6200 and the thickness ratio of the resist layer to the metal layer is 5:1.
Step S130: and (3) spot-coating conductive metal slurry on the surface of the corrosion-resistant layer to serve as a focusing point. The focus points are arranged at intervals on the periphery of a preset exposure area on the surface of the resist layer. Fig. 4 is a schematic diagram of the resist layer 230 and the focus point 240 obtained in step S130.
Because the exposure area of the large-area grating is large, the situation of poor focusing is easy to occur, the size of the photoetching pattern is deformed, and the product precision is affected. By arranging conductive metal at intervals on the periphery of the exposure area as a focusing point, the focusing condition can be improved, the photoetching precision is improved, and the problem of deformation of an etching pattern is avoided.
In some of these embodiments, the conductive metal may be selected from gold, silver, copper, tin, and the like. In an embodiment of the present invention, the conductive metal paste is silver paste.
In some of these embodiments, the spacing between adjacent focal points is 1mm to 10mm, taking into account the warpage of the sheeting and the relationship with depth of field. The focusing point interval is in this range, the electron beam focusing is good, and the exposure efficiency is high. Further, the interval between adjacent focus points is 5mm.
Step S140: the sizes of the subfields and the main fields of the electron beam equipment are adjusted to be integral multiples of the preset period of the large-area micro-nano grating to be prepared, and the field splicing lines are enabled to fall in the preset exposure area. By adjusting the sizes of the main field and the sub-field of the electron beam device to be integral multiples of the grating period and enabling the spliced lines to fall in the exposure area, the problems of strip-shaped offset, discontinuous and the like of grating ridges caused by the spliced field when preparing a large-area grating can be reduced.
In some of these embodiments, the subfield size is 1 to 73 times the preset period.
In some of these embodiments, the main field size is 1-1470 times the preset period.
For example, the grating preset period is 340nm, the subfield size of the electron beam apparatus is set to 24.82 μm, and the main field size is 499.8 μm. I.e. the sub-field size is 73 times the grating preset period and the main field size is 1470 times the grating preset period. It should be noted that the exemplary sub-field size and main field size range with respect to an integer multiple of the grating preset period are set according to the electron beam apparatus (nanobeam NB 5) employed in the embodiment of the present invention. It will be appreciated that the field size and the main field size may be adjusted to be within an integer multiple of the predetermined period of the grating, depending on the type of electron beam device used.
Step S150: and exposing and developing the resist layer to obtain a preset structure, wherein the exposure is performed by an electron beam device.
Fig. 5 is a schematic diagram of the substrate 210, the metal layer 220, and the exposed and developed resist layer 230 obtained in step S150.
In some of these embodiments, in step S150, the exposure dose is 1C/m 2 ～10C/m 2 . The acceleration voltage during exposure was 80kV. The electron beam current is 1 nA-15 nA. By performing exposure using the above parameters, the lithography pattern accuracy of the resist layer can be made to be nano-scale.
In the embodiment of the invention, the model of the electron beam equipment is nanobeam NB5. The exposure accuracy of the exposure apparatus can reach the nanometer scale.
In some of these embodiments, in step S150, development is performed using a developer. In some of these embodiments, the developer is AR 600-546 and the development time is 1min to 10min.
Step S160: and ion etching the metal layer by using the exposed and developed resist layer as a first mask. Fig. 6 is a schematic diagram of the resist layer 230, the metal layer 220, and the substrate 210 obtained in step S160.
In some of themIn an embodiment, in step S160, the etching gas includes O 2 And Cl 2 ，O 2 The flow rate of the catalyst is 10 sccm-20 sccm, and Cl 2 The flow rate of the etching solution is 30 sccm-80 sccm, and the etching power is 100W-1200W. The pressure of the cavity is 3 mTorr-15 mTorr. The bias voltage is 0-600W. At this time, the substrate may be a quartz substrate. It is to be understood that the parameters in step S160 are not limited to the above values when the substrate is other substrate or the employed device is different. Specifically, the etching time is set according to the etching rate ratio of the electron beam resist and the metal.
In some embodiments, in step S160, the parameters of the ion etching are: the etching gas is O 2 And Cl 2 O, of the mixture of (a) 2 Is 15sccm, cl 2 The flow rate of (C) was 50sccm and the etching power was 500W. The chamber pressure was 10mTorr. The bias voltage was 600W.
Step S170: and removing the corrosion-resistant layer, and carrying out ion etching on the substrate by taking the ion-etched metal layer as a second mask. Fig. 7 is a schematic diagram of the metal layer 220 and the substrate 210 from which the resist layer is removed. Fig. 8 is a schematic diagram of the metal layer 220 and the substrate 210 ion etched in step S170.
In some of these embodiments, photoresist is used to remove the resist. The photoresist remover is at least one selected from acetone, N-methyl pyrrolidone (NMP), N-ethyl pyrrolidone (NEP) and dibasic ester (NME).
In some of these embodiments, in step S170, the etching gas includes O 2 And CHF 3 ，O 2 The flow rate of the catalyst is 3sccm to 20sccm, and CHF 3 The flow rate of the etching solution is 30 sccm-80 sccm, and the etching power is 100W-1200W. The pressure of the cavity is 3 mTorr-15 mTorr. The bias voltage is 20W-600W. At this time, the substrate may be a quartz substrate. It is to be understood that the parameters in step S160 are not limited to the above values when the substrate is other substrate or the employed device is different.
In some embodiments, in step S170, the parameters of the ion etching are: the etching gas is O 2 And CHF 3 O, of the mixture of (a) 2 Is 10sccm, CHF 3 The flow rate of (2) is 50sccm, carvedThe etching power was 500W. The chamber pressure was 10mTorr. The bias voltage was 600W.
In some of these embodiments, after step S170, further includes: and removing the metal layer. Fig. 9 is a schematic diagram of a substrate 210 obtained by removing a metal layer, that is, a schematic diagram of a large-area micro-nano grating prepared by the above-mentioned preparation method. Through the above process, the substrate 210 has a grating structure of a large number of parallel stripe-shaped protrusions of equal width and equal pitch, i.e., grating ridges.
Specifically, a metal cleaning solution is used to remove the metal layer. Specifically, the metal cleaning liquid is at least one selected from chromium removing liquid, aqua regia and hydrochloric acid. The metal can be dissolved in the solution to remove the metal layer, but the solution does not affect the structure of the substrate and the resulting grating.
According to the preparation method of the large-area micro-nano grating, the sizes of the main field and the sub-field of the electron beam equipment are adjusted to be integral multiples of the grating period, and the spliced lines fall in the exposure area, so that the problems of strip-shaped offset, discontinuous and the like of grating ridges caused by the spliced field when the large-area grating is prepared can be reduced; by setting uniformly spaced silver paste as focusing points on the periphery of the exposure area, the problem of poor focus of large-area exposure can be solved, the precision of photoetching patterns can be improved, the area of the prepared large-area micro-nano grating can reach the level of square centimeter, and the precision of the grating can reach about 50 nm.
In addition, the preparation method of the large-area micro-nano grating has high preparation precision and high yield, and is particularly suitable for large-scale production.
The invention also provides a large-area micro-nano grating, which is prepared by the preparation method of the large-area micro-nano grating.
In some embodiments, the large-area micro-nano grating comprises a plurality of grating ridges which are arranged at intervals to form a plurality of parallel bars with equal width and equal interval. The width of the grating ridge is more than 50nm, and the grating period is more than 100nm.
The invention further provides an application of the large-area micro-nano grating in preparing intelligent glasses or optical devices.
Specifically, the large-area micro-nano grating can be used as an optical device in intelligent glasses.
The following are the specific examples section:
example 1:
the preparation process of the large-area micro-nano grating in the embodiment specifically comprises the following steps:
(1) And drawing a layout according to the large-area micro-nano grating to be prepared.
(2) First using NH 4 OH、H 2 O 2 And SC1 cleaning solution with the water volume ratio of 1:1:10 is used for cleaning the substrate for 10min, and then HCl and H are used for cleaning the substrate 2 O 2 And the SC2 cleaning solution with the volume ratio of water being 1:1:10 is used for cleaning the substrate for 10min. Baking the cleaned substrate, and finally cleaning with water and drying the substrate. The substrate is a quartz plate.
(3) A metal layer having a thickness of 50nm was formed on the substrate by vapor deposition of metallic Cr.
(4) And spin-coating an electron beam resist AR-P6200 on the substrate by using a glue coater to form a resist layer with the thickness of 250nm, and covering the surface of the metal layer.
(5) According to the preset grating period of 340nm, the sizes of the sub-field and the main field of the electron beam device are adjusted to be integral multiples of the grating period, and the field splicing line falls in the exposure area. The sub-field size is 24.82 μm, the main field size is 499.8 μm, namely the sub-field size is 73 times of the grating period, and the main field size is 1470 times of the grating period.
(6) A silver paste dot is coated on the periphery of the exposure area of the resist layer at intervals of 5mm to serve as a focusing point.
(7) Exposing the substrate containing the resist layer obtained in the step (6) in an electron beam device (model number: nanobeam NB 5), wherein the accelerating voltage in the exposure process is 80kV, the electron beam current is 10nA, and the exposure dose is 2.5C/m 2 . Then developed with AR 600-546 for 5min.
(8) Placing the substrate into an Inductively Coupled Plasma (ICP) etching system for etching, and etching the metal layer by using the etched resist layer as a mask, wherein etching gasThe body is O 2 And Cl 2 O, of the mixture of (a) 2 Is 15sccm, cl 2 The flow rate of (C) was 50sccm and the etching power was 300W. The chamber pressure was 10mTorr. The bias voltage is 0W.
(9) Removing the resist layer by using acetone as a photoresist remover, and then etching the substrate by using the etched metal layer as a mask, wherein the etching gas is O 2 And CHF 3 O, of the mixture of (a) 2 Is 5sccm, CHF 3 The flow rate of (C) was 50sccm and the etching power was 150W. The chamber pressure was 10mTorr. The bias voltage was 50W.
(10) And cleaning and removing the metal layer by using chromium removing liquid to obtain the large-area micro-nano grating.
Example 2:
the preparation process of the large-area micro-nano grating of example 2 is basically the same as that of example 1, except that: in step (6) of this embodiment, the interval between adjacent focus points is 1mm.
Example 3:
the preparation process of the large-area micro-nano grating of example 3 is basically the same as that of example 1, except that: in step (6) of this embodiment, the interval between adjacent focus points is 10mm.
Comparative example 1:
the preparation process of the large-area micro-nano grating of comparative example 1 is basically the same as that of example 1, except that: in step (3) of this comparative example, the thickness of the metal layer was 20nm.
Comparative example 2:
the preparation process of the large-area micro-nano grating of comparative example 2 is basically the same as that of example 1, except that: in step (5) of this comparative example, the splice line falls in the middle of the non-exposed region.
Comparative example 3:
the preparation process of the large-area micro-nano grating of comparative example 3 is basically the same as that of example 1, except that: in step (5) of this comparative example, the subfield size was 73.5 times the grating period, and the main field size was 1470.5 times the grating period.
The preset circumferences of the large-area gratings of the above examples 1 to 3 and comparative examples 1 to 3 were 340nm. The process parameters during the preparation of the large area gratings of examples 1 to 3 and comparative examples 1 to 3 are shown in table 1.
TABLE 1
The large-area micro-nano gratings prepared in the above examples 1 to 3 and comparative examples 1 to 3 were observed using a Scanning Electron Microscope (SEM), and the observed morphological characteristics are recorded in table 2 below.
TABLE 2
As can be seen from the data in table 2, the large-area micro-nano grating ridges prepared in examples 1 to 3 have substantially no offset in bar shape and uniform grating groove width. The large-area micro-nano grating prepared in comparative example 1 has poor morphology of the grating due to the fact that the thickness of the metal layer is relatively small and the thickness of the metal layer is too small as a mask, and the field splicing position has errors due to the fact that the etching depth of quartz is insufficient. The large-area micro-nano grating ridges prepared in comparative example 2 and comparative example 3 have obvious errors in the shape of bars, and the grating grooves have larger or smaller widths, so that the preparation precision is poor.
Referring to fig. 10, a scanning electron microscope photograph of the large-area micro-nano-grating prepared in example 1 is shown. It can be seen that the large-area micro-nano grating ridge prepared in the embodiment 1 has good strip-shaped continuity and no obvious offset phenomenon; the width uniformity of the grating groove is good, and the preparation precision is high.
Referring to fig. 11, a scanning electron microscope photograph of the area micro-nano-grating prepared in comparative example 2 is shown. It can be seen that the error of the large-area micro-nano grating prepared in comparative example 2 is obvious, the uniformity of the width of the grating groove is poor, and the width of the grating groove at the splicing position is increased. The morphology of the area micro-nano grating prepared in the comparative example 3 is similar to that of the grating prepared in the comparative example 2, the width of the grating groove is not uniform, and the situation that the splicing position is enlarged or reduced influences the preparation precision.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present invention, which facilitate a specific and detailed understanding of the technical solutions of the present invention, but are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. It should be understood that, based on the technical solutions provided by the present invention, those skilled in the art obtain technical solutions through logical analysis, reasoning or limited experiments, all of which are within the scope of protection of the appended claims. The scope of the patent is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted as illustrative of the contents of the claims.
Claims (9)
1. The preparation method of the large-area micro-nano grating is characterized by comprising the following steps of:
forming a metal layer on a substrate; the thickness of the metal layer is 30 nm-80 nm;
forming a resist layer on the substrate and the metal layer, wherein the resist layer covers the metal layer;
spot-coating conductive metal slurry on the surface of the corrosion-resistant layer to serve as a focusing point; the focusing points are arranged at intervals on the periphery of a preset exposure area on the surface of the resist layer;
the sizes of a sub-field and a main field of the electron beam equipment are adjusted to be integral multiples of a preset period of the large-area micro-nano grating to be prepared, and a field splicing line falls in the preset exposure area; the size of the sub-field is 1-73 times of the preset period, and/or the size of the main field is 1-1470 times of the preset period; exposing and developing the resist layer to obtain a preset structure, wherein the exposure is performed by the electron beam equipment;
ion etching is carried out on the metal layer by taking the exposed and developed anti-corrosion layer as a first mask;
and removing the corrosion-resistant layer, and carrying out ion etching on the substrate by taking the metal layer subjected to ion etching as a second mask.
2. The method for manufacturing a large-area micro-nano grating according to claim 1, wherein the interval between adjacent focusing points is 1mm to 10mm.
3. The method for producing a large area micro-nano grating according to claim 1, wherein the thickness of the resist layer is 200nm to 300nm.
4. The method for manufacturing a large-area micro-nano grating according to claim 1, wherein the material of the metal layer is at least one selected from chromium, aluminum and titanium.
5. The method of manufacturing a large area micro-nano grating according to any one of claims 1 to 4, wherein in the exposing and developing steps of the resist layer, the exposure dose is 1C/m 2 ～10C/m 2 。
6. The large area micro-nano grating according to any one of claims 1-4The method is characterized in that in the step of ion etching the metal layer by using the exposed and developed resist layer as a first mask, the etching gas comprises O 2 And Cl 2 The O is 2 The flow rate of the solution is 10sccm to 20sccm, the Cl 2 The flow rate of the etching solution is 30 sccm-80 sccm, and the etching power is 100W-1200W.
7. The method of fabricating a large area micro-nano grating according to any one of claims 1 to 4, wherein in the step of ion etching the substrate using the ion etched metal layer as the second mask, the etching gas comprises O 2 And CHF 3 The O is 2 The flow rate of the CHF is 3sccm to 20sccm 3 The flow rate of the etching solution is 30 sccm-80 sccm, and the etching power is 100W-1200W.
8. A large-area micro-nano grating, characterized in that the large-area micro-nano grating is prepared by the preparation method of the large-area micro-nano grating according to any one of claims 1-7.
9. The use of the large area micro-nano grating of claim 8 in the preparation of smart glasses or in the preparation of optical devices.
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