CN112758887A - Method for preparing sub-wavelength periodic array by mask etching - Google Patents
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- 238000005530 etching Methods 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 46
- 230000000737 periodic effect Effects 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 71
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011521 glass Substances 0.000 claims abstract description 38
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 29
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000001020 plasma etching Methods 0.000 claims abstract description 5
- 239000005368 silicate glass Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 3
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- 238000002604 ultrasonography Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 12
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- 238000001878 scanning electron micrograph Methods 0.000 description 4
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00214—Processes for the simultaneaous manufacturing of a network or an array of similar microstructural devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00206—Processes for functionalising a surface, e.g. provide the surface with specific mechanical, chemical or biological properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00388—Etch mask forming
- B81C1/00396—Mask characterised by its composition, e.g. multilayer masks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00388—Etch mask forming
- B81C1/00404—Mask characterised by its size, orientation or shape
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00436—Shaping materials, i.e. techniques for structuring the substrate or the layers on the substrate
- B81C1/00523—Etching material
- B81C1/00531—Dry etching
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
Abstract
The invention belongs to the field of micro-nano material optics, and particularly relates to a method for etching a sub-wavelength periodic array by modifying a mask on the surface of glass. A method for preparing a sub-wavelength periodic array by mask etching comprises the following steps: washing and drying the silicate glass sheet by using acetone, ethanol, deionized water and ethanol respectively; selecting a silicon dioxide dispersion liquid with well dispersed ethanol and ethylene glycol by using a spin coater, wherein the diameter of a silicon dioxide sphere is 200-500 nm; completing the volatilization of the solvent in the dispersion liquid; etching in a plasma etching chamber with CHF as etching gas3、CF4Any one or the combination of the two, the flow rate is 45-80sccm, and the etching power is 75-90W; and (5) cleaning and drying. The invention has the advantages that: the process is simple; uniform sub-wavelength microstructures can be prepared on the surfaces of different types of glass; the reflection reducing effect is good, the single-side air-glass reflection is effectively reduced from 5.5 percent to less than 3.2 percent, and the method is beneficial to practiceThe integration of the optical elements now takes place.
Description
Technical Field
The invention belongs to the field of micro-nano material optics, and particularly relates to a method for etching a sub-wavelength periodic array by modifying a mask on the surface of glass.
Background
Display products are an indispensable important ring in the modern information society, and as an output display tool of information, a display device participates in the interaction between human eyes and machinesAnd (5) linking. The surface reflection of the display device is a common problem of optical glass all the time, the surface reflection is caused by the refractive index difference between the refractive index of air and the refractive index of glass, and the reflection of common glass is approximately about 6% -8%. The traditional method for reducing the reflection of the glass surface is to plate a single-layer film on the glass surface, calculate to obtain the optimal film layer refractive index of 1.22, but the refractive index of the current lowest medium is about 1.35, and the single-layer film only has obvious interference cancellation effect on light with single wavelength, the light effect antireflection effect on other parts is not obvious, and the reflection reduction effect is weaker as the distance from the central wavelength is farther; therefore, the coating technology is gradually developed into multilayer coating, and an optimal refractive index matching can be obtained by regulating and controlling the material and the thickness of the multilayer coating, so that the lowest reflectivity is achieved; however, the vacuum coating technique is too costly and complicated, and the mixed coating may result in impure quality of the coated film layer and spectral deviation. The other method is similar to chemical etching, and is used for preparing disordered pits on the surface, so that the refractive index of a thin layer is gradually changed, but fluorine-containing ions in the chemical etching solution have great pollution to the environment in the treatment process, and NaHAsO4The solution has great harm to human body.
The sub-wavelength surface micro-nano structure can also be used as a refractive index gradient layer to reduce the reflection of an air-glass interface, corresponding refractive index matching can be obtained by adjusting a series of parameters of the micro-nano structure, and a certain hydrophobic anti-fouling effect is also achieved due to the existence of air gaps. The obtained anti-reflection glass can be widely applied to building curtain walls, greenhouse walls and the like, can effectively reduce light pollution and improve the utilization rate of sunlight. However, due to the limited methods for processing the microstructure, electron beam lithography EBL and focused ion beam etching FIB are not suitable for processing large-area surface micro-nano structures although micro-nano structure arrays can be accurately etched, and in addition, the processing cost is high and the process is complicated. Self-masking etching methods are also used, but the random arrangement cannot meet the subsequent specific preparation requirements.
Patent No. 201410546087.2, chinese patent "method for preparing random sub-wavelength broadband antireflection microstructure from mask", published as 2017, 5, 3, discloses a method for preparing random sub-wavelength broadband antireflection microstructure from mask, placing a glass substrate in a reaction chamber with mixed reaction gas to implement a plasma etching process, and controlling etching parameters to enable a nano-grade island-shaped polymer film generated on the surface of the glass substrate in the etching process to be used as a mask in the etching process, so that a tapered micro-nano antireflection structure with randomly distributed gradually-changed refractive index is generated on the surface of the glass substrate. The mask prepared by the method has complex steps and low antireflection rate.
Application No. 201510093021.7, published as 2015, 6/10, discloses a method for preparing black silicon by using a silica photoresist mask, and belongs to the field of solar cell preparation. In the processing process of the silicon wafer, firstly preparing photoresist containing silicon dioxide particles, then spinning the photoresist on the surface of the silicon wafer by using a spin coater to form a mask layer, taking out the mask layer, exposing the mask layer by using an exposure machine, etching the exposed silicon wafer in an acid-base solution or in a plasma environment, and forming a regular and regular textured surface on the surface of the silicon wafer after cleaning and demoulding. The suede prepared by the method is a common process in the prior art, and has a common antireflection rate.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the method for preparing the uniform surface sub-wavelength micro-nano array based on the surface silicon dioxide bead mask etching, which is efficient and low in cost, and can reduce the reflection of glass in a visible waveband to about 3%.
A method for preparing a sub-wavelength periodic array by mask etching comprises the following steps:
(1) washing and drying the silicate glass sheet by using acetone, ethanol, deionized water and ethanol respectively;
(2) selecting a silicon dioxide dispersion liquid with well dispersed ethanol and ethylene glycol by using a spin coater, wherein the diameter of a silicon dioxide sphere is 300-500 nm;
(3) completing the volatilization of the solvent in the dispersion liquid;
(4) etching in the plasma etching chamber, wherein etching gas CHF3, CF4 or the combination of the two gases have the flow of 45-80sccm and the etching power of 75-90W;
(5) and (5) cleaning and drying.
Preferably, the ultrasonic treatment of acetone, ethanol and deionized water in the step (1) is carried out for 5min-10min, and the purity of the selected solution is more than 99%.
Preferably, the mass ratio of the dispersion in the step (3) is 30: 35.
Preferably, the glass original sheet selected in the step (1) comprises any one of fused silica, K9 glass or common glass.
Preferably, before the etching in the step (4), the etching chamber is cleaned and pre-etched.
Preferably, the silica spheres in step (2) have a diameter of 350 nm.
Preferably, the diameter of the silicon dioxide pellet is 500nm, the etching gas is CHF 345 sccm and CF 415 sccm, the etching power is 75W, and the etching time is 6 min.
Preferably, the diameter of the silicon dioxide pellets is 350nm, the etching gas is CHF 345 sccm, the etching power is 75W, and the etching time is 4.5 min.
Advantageous effects
The method has the advantages that the simple sphere mask technology is utilized, the large-scale uniform and densely-arranged cylindrical array can be prepared on the surface of the substrate only by adjusting the diameter and the etching parameters of the spheres, the spheres serve as masks in the etching process, the size of the spheres can influence the period of the etching result, meanwhile, the spheres are closely related to the height of the cylindrical structure, and the concave-top regular cylindrical array is finally formed due to the collision of plasma. The uniform sub-wavelength micro-nano structure can be used as a refractive index gradient layer, so that the reflection of the glass surface is reduced; on one hand, the method does not cause environmental pollution caused by chemical etching, and on the other hand, the method is different from the method which is used by EBL or FIB and has complicated working procedures and higher cost. The method can generate periodic sub-wavelength microstructures on the surfaces of different glass materials by using a simple small ball template, and is favorable for further integration and development of optical devices; by using the technical scheme, the reflection of the glass surface can be reduced to about 3%.
Drawings
FIG. 1 is an SEM image of 500nm diameter silicon dioxide through a spin-on mask;
FIG. 2 is an SEM image of a 500nm diameter silicon dioxide mask after etching for antireflective;
FIG. 3 is a graph of the depth of recession inside the columnar array after 500nm silicon dioxide etch;
FIG. 4 is an external height view of a 500nm silicon dioxide etched columnar array;
FIG. 5 is an atomic force microscope scan of a 500nm silicon dioxide etched columnar array;
FIG. 6 is a graph of the reverse reflectance of glass having a subwavelength structure measured using an ultraviolet-visible spectrophotometer in example 1;
FIG. 7 is a graph of the reverse reflectance of glass having a subwavelength structure measured using an ultraviolet-visible spectrophotometer in example 2.
Detailed Description
The principle of the invention is as follows:
the spin coating technology is firstly adopted, the dispersion liquid is statically dripped, the dispersion liquid can be quickly and uniformly spread by utilizing centrifugal acceleration, redundant dispersion liquid can be thrown away from a substrate, and a layer of uniform film is formed on the whole substrate. The properties affecting the silica packing in the film are determined primarily by the adhesion of the dispersion to the substrate itself, the tension of the dispersion and the rotational speed of the spin coater. The rotating speed of the spin coater is adjusted according to the prepared silicon dioxide dispersion liquid, and the final optimal close-packed rotating speed is determined by a scanning electron microscope SEM, for example, the optimal close-packed rotating speed of the 500nm silicon dioxide dispersion liquid on a glass slide substrate is 5500 rpm. FIG. 1 shows an SEM image of 500nm diameter silicon dioxide through a spin-on mask; as shown in fig. 2, is an SEM image of a 500nm diameter silicon dioxide mask after etching. Carrying out plasma etching in an Oxford medium etching instrument by using the densely arranged silicon dioxide pellets as a mask; loading the reaction gas by using a high-frequency electric field to ionize the gas to form plasma; the plasma is electrically neutral, ions can be accelerated to impact the substrate under the action of an external electric field, the electrode bias is improved, the energy of the ions for bombarding the substrate is increased, the anisotropic etching is dominant, and the etching selection ratio is reduced; therefore, the etching time and bias voltage can be regulated and controlled, and proper etching gas is selected to achieve accurate etching for the mask.
Compared with self-mask etching, the cylindrical array with the top concave etched by the densely arranged silicon dioxide serving as the mask is more uniform and controllable; the ball mask is less costly and more efficient than EBL, FIB micromachining techniques. As shown in fig. 5, it is an atomic force microscope scanning image of a column array after 500nm silicon dioxide etching, fig. 3 and 4 are height distributions obtained by scanning along the horizontal line direction in fig. 5, fig. 3 is a top concave height of 17.27nm, and fig. 4 is a column outer wall height of 40.60 nm.
The size of the spin coater used in the examples was Schwan EZ4 spin coater;
the model of the Oxford medium etcher used in the examples is OxFORD INSTRUMENTS plasma Pro 100 Cobra;
the ultraviolet-visible spectrophotometer model used in the examples was SHIMADZU UV-2600.
Example 1
A fused silica glass master was used as a blank control.
And ultrasonically cleaning the fused quartz glass sheet with acetone, ethanol, deionized water and ethanol for 5min respectively, and blow-drying with a nitrogen gun.
20 mu L of silicon dioxide dispersion liquid with ethanol and glycol dispersed well is selected by a spin coater, silicon dioxide pellets with the diameter of 350nm are selected, the rotating speed of the spin coater is adjusted to 8000rpm so that the pellets are uniformly and densely arranged on the surface of the glass, and the spin coating time is 1 min.
After the solvent in the dispersion liquid is volatilized, a close-packed silicon dioxide mask is left on the surface; the solvent volatilization is accelerated by using a hot table in the process. The mass ratio of the dispersion liquid is that silicon dioxide powder, ethanol and glycol are 30: 35.
Cleaning and pre-etching the etching cavity before etching to ensure that the etching parameters reach a stable state, and then selecting different etching parameter combinations by using an oxford medium etching instrument:
no. 1: etching gas CHF345sccm, 75W power and 3min time;
no. 2: etching gas CHF345sccm, 75W power and 4.5min time;
no. 3: etching gas CHF345sccm, 75W power and 6min time;
putting the etched anti-reflection glass sheet into an ultrasonic machine to be cleaned for 10min, and drying to obtain a columnar array with a concave middle;
the surface reflection of the glass original sheet after treatment is measured by an ultraviolet-visible spectrophotometer, the result is shown in figure 6, and the reflectivity is reduced to 3.5% within the instant etching time of No. 2 of the glass original sheet with the wavelength of 400nm-600nm for 4.5 min; at the wavelength of 600nm-800nm, No. 2 and No. 3, the instant etching time is 4.5min and 6min, and the reflection is reduced to 3.5%; while the blank glass plate adopted by the control group has 5 percent of reflectivity in the visible wavelength band of 400nm-800 nm.
Example 2
A K9 glass plaque was used as a blank control.
And ultrasonically cleaning the K9 glass original sheet with acetone, ethanol, deionized water and ethanol for 5min respectively, and drying.
In the embodiment of the invention, the silicon dioxide spheres with the diameter of 500nm are selected, the rotating speed of a spin coater is adjusted to 5500rpm so that the spheres are uniformly and densely arranged on the surface of the glass, and the spin coating time is 1 min. And ultrasonically cleaning the silicate glass raw sheet with acetone, ethanol, deionized water and ethanol for 5min respectively, and blow-drying with a nitrogen gun.
20 mu L of silicon dioxide dispersion liquid with ethanol and glycol dispersed well is selected by a spin coater, silicon dioxide pellets with the diameter of 500nm are selected, the rotating speed of the spin coater is adjusted to 8000rpm so that the pellets are uniformly and densely arranged on the surface of the glass, and the spin coating time is 1 min.
After the solvent in the dispersion liquid is volatilized, a close-packed silicon dioxide mask is left on the surface; the solvent volatilization is accelerated by using a hot table in the process. The mass ratio of the dispersion liquid is that silicon dioxide powder, ethanol and glycol are 30: 35.
Cleaning and pre-etching the etching cavity before etching to ensure that the etching parameters reach a stable state, and then selecting different etching parameter combinations by using an oxford medium etching instrument:
no. 1: etching gas CHF345sccm, 75W power and 6min time;
no. 2: etching gas CHF380sccm, 75W power and 4.5min time;
no. 3: etching gas CHF345sccm and CF415sccm, power 75W and time 6 min;
putting the etched anti-reflection glass sheet into an ultrasonic machine to be cleaned for 10min, and drying to obtain a columnar array with a concave middle;
the initial 5% reflection of the treated glass master was reduced to about 3.5% as measured by an ultraviolet-visible spectrophotometer.
The results are shown in FIG. 7, which is obtained from the reflection results of the test, in which case the blank control had a reflectivity of about 5%, and 500nm pellets etched in a visible wavelength of 400nm-600nm, CHF was used as the etching gas3The optimal effect is achieved by 45sccm, 75W of power and 6min of time, and the reflectivity is between 3.5% and 4%; etching gas CHF in visible wavelength of 600nm-800nm with 500nm small ball345sccm and CF4The optimal effect is achieved by 15sccm, 75W of power and 6min of time, and the reflectivity is between 3% and 3.5%.
From the above result analysis, it can be known that there is an optimal etching time and an optimal mask diameter. When the etching time is not enough, the depth of the columnar structure formed by the un-etched mask or the etched mask is not enough; the etching time is too long, and the columnar structure is damaged and collapsed due to the obvious isotropic effect. Theoretically, the obtained broadband antireflection effect is most obvious under the condition that the obtained columnar structure has a small period and a deep depth; however, in the actual etching process, there is a balance, and the period and depth of the columnar structure are controlled by the diameter of the small ball mask, so that there is an optimum value, which is about 500nm according to the current trial result. In addition, the etching method based on the silicon dioxide mask not only can be used for reducing surface reflection, but also can be used for processing other microstructures.
Claims (8)
1. A method for preparing a sub-wavelength periodic array by mask etching is characterized by comprising the following steps:
(1) washing and drying the silicate glass sheet by using acetone, ethanol, deionized water and ethanol respectively;
(2) selecting a silicon dioxide dispersion liquid with well dispersed ethanol and ethylene glycol by using a spin coater, wherein the diameter of a silicon dioxide sphere is 300-500 nm;
(3) completing the volatilization of the solvent in the dispersion liquid;
(4) etching in a plasma etching chamber with CHF as etching gas3、CF4Any one or the combination of the two, the flow rate is 45-80sccm, and the etching power is 75-90W;
(5) and (5) cleaning and drying.
2. The method for preparing the sub-wavelength periodic array by mask etching according to claim 1, wherein the ultrasound of acetone, ethanol and deionized water in the step (1) is 5min to 10min, and the purity of the selected solution is more than 99%.
3. The method for preparing the sub-wavelength periodic array by mask etching according to claim 1, wherein the mass ratio of the dispersion liquid in the step (3) is silicon dioxide powder: ethanol: ethylene glycol 30: 35: 35.
4. the method for preparing the sub-wavelength periodic array by mask etching according to claim l, wherein the glass original sheet selected in the step (1) comprises any one of fused silica, K9 glass or common glass.
5. The method for preparing the sub-wavelength periodic array by mask etching according to claim 1, wherein before the etching in the step (4), the etching chamber is cleaned and pre-etched.
6. The method for preparing the sub-wavelength periodic array by mask etching according to claim 1, wherein the diameter of the silica spheres in the step (2) is 350 nm.
7. The method of claim 1, wherein the silicon dioxide spheres have a diameter of 500nm and the etching gas is CHF345sccm and CF415sccm, an etching power of 75W and an etching time of 6 min.
8. The method of claim 1, wherein the silicon dioxide spheres have a diameter of 350nm, and the etching gas is CHF (CHF)345sccm, an etching power of 75W and an etching time of 4.5 min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117510097A (en) * | 2023-12-29 | 2024-02-06 | 核工业西南物理研究院 | Silicon-based ceramic surface metallization method and application |
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| CN101308219A (en) * | 2008-06-27 | 2008-11-19 | 吉林大学 | Method for constructing anti-reflection microstructure using single layer nanometer particle as etching blocking layer |
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