CN115308828A - Preparation method of titanium dioxide grating and titanium dioxide grating - Google Patents
Preparation method of titanium dioxide grating and titanium dioxide grating Download PDFInfo
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Abstract
The invention provides a preparation method of a titanium dioxide grating and the titanium dioxide grating, relating to the technical field of preparation methods of photoelectric devices; the preparation method comprises the following steps: providing a substrate and a master plate with a titanium dioxide grating pattern; sequentially forming a titanium dioxide film layer and an impression glue layer on the substrate; transferring the pattern on the master plate to a titanium dioxide film layer by utilizing the processes of imprinting and etching to form a titanium dioxide grating; wherein, other etching barrier layers are not arranged on the titanium dioxide film layer and the imprinting adhesive layer; the aspect ratio of the titanium dioxide grating is 1/6 to 1/2. The titanium dioxide grating manufacturing method can obtain the titanium dioxide grating structure with the side wall inclination angle close to 90 degrees, and other top layer materials except the imprinting glue layer do not need to be added on the titanium dioxide film layer in the manufacturing process, so that the titanium dioxide grating manufacturing process is simplified, and the manufacturing cost is reduced.
Description
Technical Field
The invention relates to the technical field of photoelectric device preparation methods, in particular to a titanium dioxide grating preparation method and a titanium dioxide grating thereof.
Background
With the rise of virtual reality in recent years, the technology behind the virtual reality, namely, the diffractive optical waveguide, is gradually a research and development hotspot. In order to transmit the virtual image generated by the optical machine to human eyes through the optical waveguide, a process of coupling light into and out of the waveguide is required, and a traditional optical structure above millimeter level needs a plurality of groups of lenses to perform optical imaging compounding to obtain a miniaturized optical structure, so that the process is extremely difficult to realize, and a more miniaturized optical structure is required. The appearance of the diffraction grating expands the traditional optical structure from millimeter level to micro-nano level, and turns from 'three-dimensional' to 'plane', and the diffraction grating is processed after a layer of thin film is plated on the plane of the glass substrate, so that the processes of glass slicing, multilayer film, bonding and the like are not needed like the traditional optical structure of the geometric optical waveguide, and the mass production and the yield of the diffraction optical waveguide are improved.
In order to achieve a good imaging effect, the diffraction light waveguide also requires that the diffraction grating has good light-emitting uniformity, and the light-emitting uniformity of the diffraction grating is related to the design parameters (such as duty ratio, grating shape and grating material) of the grating, so that the control on the light-emitting uniformity of the grating can be realized by changing the design parameters of the grating. In the grating material, titanium dioxide (TiO) 2 ) Because the material has good electrical and optical characteristics and the band gap energy is just slightly higher than 2 times of single photon energy in the visible wavelength range, the material has weak two-photon absorption and low price, and is often selected as the best material for researching optical waveguides; with the advent of micro-nano technology, tiO is prepared 2 The two-dimensional columnar grating with the micro-nano structure, the inclined grating and the triangular blazed grating become possible. Furthermore, for TiO 2 For a columnar grating, tiO 2 The ideal value of the inclination angle of the side wall of the micro-nano structure is 90 degrees, and generally can not be lower than 75 degrees because of TiO 2 The inclination angle of the side wall of the micro-nano structure is smaller than 75 degrees, so that the light efficiency is influenced, the light of adjacent units is coherent, and the effect of coupling the light from the optical waveguide diffraction light is reduced. Therefore, tiO with an inclination angle of not less than 75 DEG 2 The grating becomes a micro-nano grating structure which can meet the requirements of diffraction light waveguide at present, and has better research and development and application prospects.
At present TiO 2 The grating structure is prepared mainly by TiO 2 Is obtained by combining a micro-nano process and dry etching, and is due toTiO 2 The etching difficulty is high, top layer materials such as a metal mask and the like are needed in the etching process, for example, a metal layer is deposited on the titanium dioxide film layer to be used as a mask material, and an ideal TiO2 grating structure is finally obtained by controlling the difference of the etching rates of the metal layer and the titanium dioxide in the etching process. For example, in the titanium dioxide etching process mentioned in patent CN113097343A, a metal layer is deposited on a titanium dioxide film, a layer of imprinting glue is spin-coated on the metal layer, and a micro-nano structure pattern is obtained on the upper surface of the imprinting glue by using a nano-imprinting method. Firstly, etching the imprinting adhesive and the metal layer, and then etching the metal layer and the titanium dioxide film to obtain titanium dioxide in a micro-nano structure pattern; in addition, as a vertical etching process for preparing titanium dioxide with high aspect ratio disclosed in patent CN110347014A, mention is made of: plating titanium dioxide on the ITO glass, spinning and coating a layer of photoresist on the titanium dioxide, plating a layer of metal mask on the photoresist, and achieving vertical etching by adopting different etching rates on the titanium dioxide and the metal mask. The process of preparing the metal mask layer involves a multi-step process such as deposition of a metal layer, exposure of a photoresist, development, fixing, etching of the metal layer, etc., thereby making the TiO layer 2 The grating preparation process is complicated, and the production cost is improved.
Disclosure of Invention
The application aims to provide a preparation method of a titanium dioxide grating, the titanium dioxide grating structure with the side wall inclination angle close to 90 degrees can be prepared through processes of stamping, etching and the like, stamping glue is used as an etching mask material, top layer materials such as other metal layers and the like do not need to be added on a titanium dioxide film layer, the production process of the titanium dioxide grating is simplified, and the production cost is reduced.
It is yet another object of the present application to provide a titanium dioxide grating.
Based on the technical problem, the application provides a preparation method of a titanium dioxide grating, which comprises the following steps:
providing a substrate and a master plate with a titanium dioxide grating pattern;
sequentially forming a titanium dioxide film layer and an imprinting adhesive layer on the substrate, wherein the thickness of the imprinting adhesive layer is not less than 200nm;
transferring the pattern on the master plate to a titanium dioxide film layer by utilizing the processes of impressing and etching to form a titanium dioxide grating;
wherein, the titanium dioxide film layer and the impression glue layer are not provided with an etching barrier layer; the aspect ratio of the titanium dioxide grating is 1/6 to 1/2; the aspect ratio is the ratio of the grating height to the grating width of any grating unit in the titanium dioxide grating.
Further, in some embodiments of the present application, the thickness of the imprinting adhesive layer is 2 to 20 times of the thickness of the titanium dioxide film layer.
Further, in some embodiments of the present application, the processing gas in the etching process includes an etching gas for etching titanium dioxide and a protective gas for preventing the sidewalls of the grating units of the titanium dioxide grating from being etched by the etching gas, the protective gas is hydrogen halide, and a ratio of an etching rate of the etching gas to the titanium dioxide film layer to an etching rate of the etching gas to the imprint glue layer is not less than 1.
Further, in some embodiments of the present application, the etching process is a dry etching process, and the dry etching process includes:
adjusting the technological parameters of the dry etching process according to the longitudinal width ratio of the titanium dioxide grating to be obtained; the ratio of the etching rate of the etching gas to the titanium dioxide film layer to the etching rate of the etching gas to the imprinting glue layer is not less than 1.
Further, in some embodiments of the present application, the process parameters include a ratio of hydrogen halide in the etching gas, a gas flow rate of hydrogen halide, a pressure in a chamber in which the dry etching process is performed, and a source power used by an apparatus in which the dry etching process is performed.
Further, in some embodiments of the present application, the ratio of the etching gas to the hydrogen halide is 1 to 3; and/or
The gas flow of the etching gas is 20 to 300SCCM; the gas flow of the hydrogen halide is 50 to 300SCCM; and/or
The pressure in the cavity for carrying out the dry etching process is 5 to 100mTorr; and/or
The source power adopted by the equipment for carrying out the dry etching process is 100-500w.
Further, in some embodiments of the present application, the etching gas is selected from one or more of a fluorocarbon gas, a nitrogen-fluorine gas, and a sulfur-fluorine gas; and/or
The hydrogen halide is one or more selected from hydrogen bromide, hydrogen chloride and hydrogen fluoride.
Further, in some embodiments of the present application, after forming the titanium dioxide grating, the method further comprises: removing the mask plate and the residual imprinting adhesive layer;
wherein removing the remaining imprint resist layer comprises:
and removing the imprinting glue layer on the titanium dioxide grating by using a dry photoresist removing process and/or a wet process.
Further, in some embodiments of the present application, the titanium dioxide film layer is deposited on the substrate using a thin film process; the film process is selected from one or more of ALD technology, magnetron sputtering, electron beam evaporation, chemical vapor deposition and sol-gel method; and/or
The imprinting glue layer is formed on the titanium dioxide film layer using one or more of a slit coating process, a spray coating process, a spin coating process, and a roll-to-roll coating process.
The application also provides a titanium dioxide grating which is prepared by the preparation method of the titanium dioxide grating.
The application provides a preparation method of a titanium dioxide grating, which utilizes an imprinting adhesive layer with the thickness not less than 200nm as an etching barrier layer to protect the side wall of a grating unit of the titanium dioxide grating in the etching process, and does not need to additionally arrange the etching barrier layer to protect the side wall of the grating unit, thereby omitting the process steps of forming, etching, removing and the like of the etching barrier layer in the prior art, simplifying the preparation process and reducing the production cost; meanwhile, the number of film layers and process steps on the titanium dioxide film layer are reduced, so that the influence of processes such as forming, etching and removing of an etching barrier layer on the titanium dioxide grating is reduced, the yield of the titanium dioxide grating is improved, and the performance of the titanium dioxide grating is improved and the titanium dioxide grating is popularized and used; the method is suitable for preparing the grating structure with low longitudinal-to-width ratio, and the grating with the side wall inclination angle close to 90 degrees can be prepared by directly using the imprinting glue as a barrier layer by controlling the thickness of the imprinting glue and the proportion of the imprinting glue to the thickness of the grating and the etching ratio of the imprinting glue to a titanium dioxide layer in the etching process.
The titanium dioxide grating is simple in preparation process, good in performance consistency and convenient to popularize and use.
Drawings
In order to more clearly illustrate the detailed description of the present application or the technical solutions in the prior art, the drawings needed to be used in the detailed description of the present application or the prior art description will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic top view of a semi-finished device provided in an embodiment of the present application;
FIG. 2 isbase:Sub>A schematic cross-sectional view taken along line A-A ofbase:Sub>A semi-finished device provided by an embodiment of the present application;
FIG. 3 is a schematic cross-sectional view of a device resulting from etching of the semi-finished device of FIG. 2;
FIG. 4 is a schematic cross-sectional view of the device of FIG. 3 after photoresist stripping;
FIG. 5 is a scanning electron microscope image of a cross section of a semi-finished device (before etching) provided by an embodiment of the present application;
FIG. 6 is a scanning electron microscope image of the etched cross-section of the semi-finished device of FIG. 5;
FIG. 7 is a scanning electron microscope cross-sectional view of an etched semi-finished device as provided in comparative example 1 of the present application;
FIG. 8 is a scanning electron microscope cross-sectional view of an etched semi-finished device as provided in comparative example 2 of the present application;
FIG. 9 is a scanning electron microscope cross-sectional view of an etched semi-finished device as provided in comparative example 4 of the present application;
fig. 10 is a top view of a semi-finished device as provided in comparative example 4 of the present application.
Description of the main element symbols:
10-a glass substrate, 20-a titanium dioxide film layer and 30-an imprinting glue layer; 40-grating unit.
Detailed Description
The technical solutions of the present application will be described clearly and completely with reference to the following embodiments, and it should be apparent that the described embodiments are some, but not all, embodiments of the present application. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. 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.
The following disclosure provides many different embodiments or examples for implementing different features of the application. To simplify the disclosure of the present application, specific example components and arrangements are described below. Of course, they are merely examples and are not intended to limit the present application. Moreover, the present application may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. Additionally, examples of various specific materials are provided herein, but one of ordinary skill in the art may recognize the application of other processes and/or the use of other materials.
The application provides a preparation method of a titanium dioxide grating, which comprises the following steps:
providing a substrate and a master plate with a titanium dioxide grating pattern;
sequentially forming a titanium dioxide film layer and an imprinting adhesive layer on the substrate, wherein the thickness of the imprinting adhesive layer is not less than 200nm;
transferring the pattern on the mask plate to a titanium dioxide film layer by using imprinting and etching processes to form a titanium dioxide grating;
wherein, the titanium dioxide film layer and the impression glue layer are not provided with etching barrier layers; the aspect ratio of the titanium dioxide grating is 1/6 to 1/2; the aspect ratio is the ratio of the grating height to the grating width of any grating unit in the titanium dioxide grating.
It should be noted that, in the present application, the titanium dioxide grating is formed by arranging a plurality of grating units which are uniformly distributed, and adjacent grating units form a groove; each grating unit is enclosed by a top surface and four side walls.
Due to the arrangement of the titanium dioxide film layer and the imprinting glue layer, after imprinting, the imprinting glue and the titanium dioxide film layer are etched by using etching gas, and in the etching process, the imprinting glue is used as an etching mask to gradually form grating units of the titanium dioxide grating. In the process, the thickness of the imprinting glue is strictly controlled, so that the imprinting glue not only can play a role in transferring the titanium dioxide grating pattern, but also can play a role in etching blocking, and the preparation of the titanium dioxide grating structure is realized. The application provides a preparation method of a titanium dioxide grating suitable for low aspect ratio, the thickness of an imprinting adhesive layer is adjusted, so that the imprinting adhesive layer not only can be used as a film layer required by transferring a titanium dioxide grating pattern, but also can be used as an etching barrier layer, and the requirement that the inclination angle of the side wall of a grating unit is not lower than 75 degrees can be met without additionally arranging the etching barrier layer; in addition, the imprinting adhesive layer is used as the film layer and the etching barrier layer required by the transfer of the titanium dioxide grating pattern, so that the process steps and the preparation cost required by forming other etching barrier layers in the prior art can be omitted, the production cost of the titanium dioxide grating is reduced, and the production efficiency of the titanium dioxide grating is improved. In addition, the thickness of the imprinting adhesive layer is not less than 200nm, so that the imprinting adhesive layer is kept stable in the etching process, the edge is not easy to collapse, and the etching result is influenced.
In the application, the etching barrier layer is understood to be a layer structure which has an etching barrier effect and is other than the imprinting glue layer; such as a metal film layer and a silicon dioxide film layer.
In some embodiments, the imprint resist is a nanoimprint resist, which may be selected from any one or more of commercially available hot-press nanoimprint resists, thermoplastic nanoimprint resists, ultraviolet-curable nanoimprint resists, and photo-resist resists.
In some embodiments, the substrate may be selected from one or more of a silicon substrate, a silicon dioxide substrate, a glass substrate, a sapphire substrate.
In some embodiments, the reticles employed in the present application are nanoimprint templates.
In some embodiments, the thickness of the imprinting adhesive layer is 2 to 20 times of that of the titanium dioxide film layer, because the imprinting adhesive layer and the titanium dioxide film layer are etched under the action of bias voltage of plasma in an etching process, but the etching rate of the imprinting adhesive layer by the plasma is high, so that the imprinting adhesive layer with the low thickness cannot play a good mask role easily; meanwhile, the phenomenon that the thickness of the imprinting adhesive layer is too thick is avoided, because the too thick imprinting adhesive layer is easy to cause that the imprinting adhesive layer is not easy to demould in the imprinting process, the edges and corners of the imprinted patterns are not clear enough, and the appearance of the etched titanium dioxide grating is influenced; preferably, the thickness of the stamping glue layer is 3 to 10 times of that of the titanium dioxide film layer.
In some embodiments, the processing gas in the etching process comprises an etching gas for etching titanium dioxide and a protective gas for preventing the sidewalls of the grating units of the titanium dioxide grating from being etched by the etching gas, wherein the protective gas is hydrogen halide; the ratio of the etching rate of the etching gas to the titanium dioxide film layer to the etching rate of the etching gas to the imprinting glue layer is not less than 1.
In the application, hydrogen halide gas is used as protective gas, the proportion of the etching gas to the protective gas is controlled to avoid isotropic etching, and the side wall is passivated and protected by the hydrogen halide gas to obtain a grating unit structure with the side wall inclination angle close to 90 degrees. The side surface inclination angle of the finally obtained titanium dioxide grating can reach more than 80 degrees, and the optical requirement of the titanium dioxide grating is met; meanwhile, other etching barrier layers required in the prior art, such as a metal film layer, are omitted; meanwhile, other etching barrier layers, such as deposition process of a metal film layer, photoresist exposure, development, metal film layer etching and other processes, and subsequent removal of the metal film layer and other processes are omitted, so that the preparation steps of the titanium dioxide grating are reduced, the preparation efficiency and raw materials are improved, and the preparation cost of the titanium dioxide grating is reduced; meanwhile, the influence of the process on the yield of the titanium dioxide optical grating is avoided, and the performance of the titanium dioxide optical grating is improved.
In some embodiments, the etching process is a dry etching process, the dry etching process comprising:
adjusting the technological parameters of the dry etching process according to the longitudinal width ratio of the titanium dioxide grating to be obtained; the ratio of the etching rate of the etching gas to the titanium dioxide film layer to the etching rate of the etching gas to the imprinting glue layer is not less than 1;
the aspect ratio is the ratio of the grating height to the grating width of any grating unit in the titanium dioxide grating.
TiO 2 The longitudinal-to-width ratio of the grating structure affects the etching process selection and the etching effect. For example, for a grating with a large longitudinal width ratio, the required thickness of the imprinting adhesive mask layer is large, and the formed pore structure is deep, which can affect the etching of the titanium dioxide by etching gas in the subsequent etching process. The process conditions of the embodiment are suitable for the grating structure with the longitudinal-to-width ratio of 1/6 to 1/2. In order to ensure that the inclination angle of the side wall of the grating unit of the prepared titanium dioxide grating meets the requirement, in the preparation method provided by the application, the range value of the process parameter of the dry etching process is set according to the longitudinal width ratio of the titanium dioxide grating to be obtained, and then one or more process parameters of the dry etching process are finely adjusted, so that the etching rate of the etching gas on the titanium dioxide film layer and the etching rate of the imprinting glue layer are not less than 1, and the inclination angle and other parameters of the side wall of the grating unit of the obtained titanium dioxide grating meet the requirement.
In some embodiments, the process parameters include a proportion of hydrogen halide in the etching gas, a gas flow rate of the hydrogen halide, a pressure within a chamber in which the dry etching process is performed, and a source power used by an apparatus in which the dry etching process is performed.
In some embodiments, the process parameters further include a temperature within a chamber in which the dry etch process is performedThe temperature, the bias power adopted by equipment for carrying out the dry etching process, the etching time for carrying out the dry etching process and the like, wherein the temperature in a cavity for carrying out the dry etching process can be selected from 20 to 100 ℃, and preferably from 50 to 100 ℃; the bias power adopted by the equipment for carrying out the dry etching process can be selected from 0 to 200w, and preferably from 50 to 200w; the etching time of the dry etching process can be selected from 60 to 180s; wherein the etching time is in accordance with TiO 2 The longitudinal-width ratio of the grating unit of the grating is adjusted, and the etching time is longer when the value of the longitudinal-width ratio is larger.
In some embodiments, the ratio of the etching gas to the hydrogen halide is 1 to 3 to 5 by mass; and/or
The gas flow of the etching gas is 20 to 300SCCM; the gas flow of the hydrogen halide is 50 to 300SCCM; and/or
The pressure in the chamber for carrying out the dry etching process is 5 to 100mTorr; and/or
The source power adopted by the equipment for carrying out the dry etching process is 100-500w.
In some embodiments, the gas flow of the etching gas is preferably 40 to 250SCCM; the gas flow rate of the hydrogen halide is preferably 50 to 250SCCM; and/or
The pressure in the cavity for carrying out the dry etching process is preferably 5 to 80mTorr; and/or
The source power adopted by the equipment for carrying out the dry etching process is preferably 100 to 300w.
It should be noted that "SCCM" is a unit of gas mass flow, and SCCM (Standard Cubic meter per Minute) is a Standard milliliter per Minute; mTorr is the unit of pressure. mTorr is the pressure of micromillimeter mercury, one thousandth of the pressure of millimetre mercury, 1mTorr equals 0.133Pa.
In some embodiments, the etching gas is selected from one or more of a fluorocarbon gas, a nitrogen-fluorine gas, and a sulfur-fluorine gas; and/or
The hydrogen halide is one or more selected from hydrogen bromide, hydrogen chloride and hydrogen fluoride.
In some embodiments, the etching gas is selected from one or more of nitrogen fluoride, carbon tetrafluoride, and sulfur hexafluoride.
Preferably, the etching gas is carbon tetrafluoride; the hydrogen halide is selected from hydrogen bromide.
In some embodiments, after forming the titanium dioxide grating, further comprising: and removing the mask plate and the residual imprinting adhesive layer.
In some embodiments, removing the reticle and the remaining layer of imprint glue comprises:
removing the mask;
and removing the imprinting glue layer on the titanium dioxide grating by using a dry photoresist removing process and/or a wet process.
In some embodiments, removing the reticle and the remaining imprint glue layer comprises:
removing the mask;
and sequentially removing the imprinting adhesive layer on the titanium dioxide grating by using a dry photoresist removing process and a wet photoresist removing process.
In some embodiments, the dry stripping process comprises: removing the imprinting glue layer on the technological titanium dioxide grating by using a process gas at the temperature of 20 to 300 ℃; wherein the process gas comprises oxygen, hydrogen, nitrogen, or the process gas comprises oxygen and nitrogen. Wherein the flow of oxygen is 1000 to 5000SCCM, preferably 3000SCCM; wherein the flow rates of the hydrogen and the nitrogen are respectively 100 to 500SCCM, and preferably 500SCCM.
In some embodiments, the temperature of the dry stripping process is preferably 20 to 250 ℃.
In some embodiments, the wet strip process is selected from a solvent strip or an oxide strip.
In some embodiments, the solvent used in the wet stripping process comprises acetone, isopropanol and ultrapure water in a mass ratio of 1; the time for wet stripping with solvent is 5min.
In some embodiments, the titanium dioxide film layer is deposited on the substrate using a thin film process; the film process is selected from one or more of ALD (atomic layer deposition) technology, magnetron sputtering, electron beam evaporation, chemical vapor deposition and sol-gel method; and/or
The imprinting glue layer is formed on the titanium dioxide film layer using one or more of a slit coating process, a spray coating process, a spin coating process, and a roll-to-roll coating process.
The application also provides a titanium dioxide grating which is prepared by the preparation method of the titanium dioxide grating.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
The embodiment provides a method for preparing a titanium dioxide grating, which comprises the following steps:
s1: selecting a glass substrate 10, and cleaning the glass substrate 10 by using HF (hydrogen fluoride) aqueous solution and deionized water to remove impurities on the surface of the glass substrate;
s2, depositing a titanium dioxide film layer 20 with the thickness of 80nm on the glass substrate 10 by using an ALD technology; wherein, the gaseous source is selected from titanium chloride and water vapor, and the temperature is 150 ℃;
s3, coating a layer of ultraviolet light curing glue on the titanium dioxide film layer 20 in a spinning mode to obtain a stamping glue layer 30 with the thickness of 300 nm;
s4: by making use of preformed TiO 2 The nano-imprinting master mask with the grating mask pattern is used for imprinting the imprinting adhesive layer 30, and the imprinting adhesive is cured and developed through ultraviolet irradiation to enable TiO 2 Transferring the grating mask pattern to the imprinting glue layer 30 to obtain a semi-finished device, referring to fig. 1 and 2;
s5: applying ESC voltage and controlling He flow to make the semi-finished device be electrostatically adsorbed in the process chamber of the etching equipment; performing dry etching on the semi-finished device for 100s by using Inductively Coupled Plasma (ICP), wherein the temperature of the chamber is 60 ℃, the pressure of the chamber is 8mTorr, and HBr/(HBr + CF) is 4 ) The proportion is 3 2 The ratio of the etched etching rate/the etched etching rate of the imprint resist is about 2; in this embodiment, the aspect ratio of the grating unit 40 of the titanium dioxide grating to be obtained is 1/4; the source power of the glow starting etching is 250W, and the bias power is 100W;
removing the adsorption voltage of the semi-finished device after the etching is finished, completely removing the electrostatic adsorption of the semi-finished device through inflation and radio frequency treatment, and taking out the semi-finished device to obtain a titanium dioxide grating device, and referring to fig. 3;
s6, fixing the device of the obtained titanium dioxide grating in a process cavity of a photoresist removing device, introducing oxygen at the temperature of 250 ℃ in the process cavity according to the flow of 3000SCCM and nitrogen at the flow of 500SCCM, and performing photoresist removing treatment for 2min; then transferring the device after photoresist removal treatment to a mixed solution of acetone, isopropanol and ultrapure water, and rinsing for 2min to remove residual photoresist and other organic impurities; and then washed with ultrapure water for 3min to obtain the product, see figure 4.
Example 2
The embodiment provides a method for preparing a titanium dioxide grating, which comprises the following steps:
s1: selecting a silicon substrate, and cleaning the silicon substrate by using HF (hydrogen fluoride) aqueous solution and deionized water to remove impurities on the surface of the silicon substrate;
s2, depositing a titanium dioxide film layer 20 with the thickness of 100nm on the silicon substrate by using an ALD technology;
s3, coating a layer of ultraviolet curing impression glue on the titanium dioxide film layer 20 in a spinning mode to obtain an impression glue layer 30 with the thickness of 200nm;
s4: imprinting the imprinting adhesive layer 30 by using a nano imprinting master plate prefabricated with a titanium dioxide grating pattern, curing and developing the imprinting adhesive through ultraviolet irradiation, and transferring the titanium dioxide grating pattern onto the imprinting adhesive layer 30 to obtain a semi-finished device;
s5: applying ESC voltage and controlling He flow to make the semi-finished device be electrostatically adsorbed in the process chamber of the etching equipment; performing dry etching on the semi-finished device for 120s by utilizing ICP (inductively coupled plasma), wherein the chamber temperature is 60 ℃, the chamber pressure is 8mTorr, and HBr/(HBr + CF) is 4 ) The proportion is 3:4,TiO 2 2 The etched etching rate/etched etching rate of the imprint resist is 1; in this embodiment, the value of the longitudinal-to-width ratio of the grating unit 40 of the titanium dioxide grating to be obtained is 1/4; the source power of the glow starting etching is 250W, and the bias power is 100W;
removing the adsorption voltage of the semi-finished device after the etching is finished, completely removing the electrostatic adsorption of the semi-finished device through air inflation and radio frequency treatment, and taking out the semi-finished device to obtain a titanium dioxide grating device, and referring to fig. 3;
s6, fixing the device of the obtained titanium dioxide grating in a process cavity of a photoresist removing device, introducing oxygen according to 3000SCCM flow and nitrogen according to 500SCCM flow in the process cavity at 250 ℃, and performing photoresist removing treatment for 2min; then transferring the device after photoresist removal treatment to a mixed solution of acetone, isopropanol and ultrapure water, and rinsing for 2min to remove residual photoresist and other organic impurities; and then the mixture is cleaned for 3min by ultrapure water to obtain the product.
Example 3
The embodiment provides a method for preparing a titanium dioxide grating, which comprises the following steps:
s1: selecting a silicon substrate, and cleaning the silicon substrate by using HF (hydrogen fluoride) aqueous solution and deionized water to remove impurities on the surface of the silicon substrate;
s2, depositing a titanium dioxide film layer 20 with the thickness of 80nm on a silicon substrate by utilizing an ALD technology;
s3, coating a layer of ultraviolet curing impression glue on the titanium dioxide film layer 20 in a spinning mode to obtain an impression glue layer 30 with the thickness of 1600 nm;
s4: by making use of preformed TiO 2 The nano imprinting master plate of the grating pattern imprints the imprinting adhesive layer 30, and the imprinting adhesive is cured and developed through ultraviolet irradiation, so that the titanium dioxide grating pattern is transferred to the imprinting adhesive layer 30 to obtain a semi-finished device;
s5: applying ESC voltage and controlling He flow rate to enable the semi-finished device to be electrostatically adsorbed in a process chamber of the etching equipment; performing dry etching on the semi-finished device for 120s by using ICP etching technology, wherein the chamber temperature is 60 ℃, and the chamber pressure is 8mTorr, HBr/(HBr + CF) 4 ) The proportion is 3:8,TiO 2 The ratio of the etched etching rate/the etched etching rate of the imprint resist is about 3; in this embodiment, the aspect ratio of the grating unit 40 of the titanium dioxide grating to be obtained is 1/4; the source power of the starting etching is 300W, and the bias power is 150W;
removing the adsorption voltage of the semi-finished device after the etching is finished, completely removing the electrostatic adsorption of the semi-finished device through air inflation and radio frequency treatment, and taking out the semi-finished device to obtain a titanium dioxide grating device, and referring to fig. 3;
s6, fixing the device of the obtained titanium dioxide grating in a process cavity of a photoresist removing device, introducing oxygen according to 3000SCCM flow and nitrogen according to 500SCCM flow in the process cavity at 250 ℃, and performing photoresist removing treatment for 2min; then transferring the device after photoresist removal treatment to a mixed solution of acetone, isopropanol and ultrapure water, and rinsing for 2min to remove residual photoresist and other organic impurities; and then the mixture is cleaned for 3min by ultrapure water to obtain the product.
Comparative example 1
In this comparative example, the thickness of the imprint resist layer deposited in S3 was 100nm, compared to example 1; the remaining procedure was the same as in example 1, to obtain comparative sample 1.
Comparative example 2
In this comparative example, HBr/(HBr + CF) in S5 is compared to example 2 4 ) The proportion is 3:3.5; the remaining procedure was the same as in example 1, to obtain comparative sample 2.
Comparative example 3
In this comparative example, HBr/(HBr + CF) in S5 is comparable to example 2 4 ) The proportion is 3:9; the remaining procedure was the same as in example 1, to obtain comparative sample 3.
Comparative example 4
In this comparative example, HBr and CF were adjusted in S5 as compared to example 1 4 Flow rate and ratio of (A) to (B), etch rate of the imprint resist to be etched/TiO 2 The ratio of the etch rates being etched is about 2; the remaining procedure was the same as in example 1, yielding comparative sample 4.
The semi-finished devices before etching and the devices after etching obtained in the embodiments 1 to 3 and the comparative examples 1 to 4 are characterized by using an electronic scanning electron microscope, and the characterization results are shown in fig. 5 to 10.
As can be seen from fig. 5 and 6, the sidewall of the grating unit of the titania grating obtained by the method for preparing a titania grating provided by the present application is not etched significantly, and the sidewall inclination angle of the grating unit 40 can reach over 84 °, which meets the requirement of the sidewall inclination angle of the titania grating. Thus, the TiO provided by the application 2 Method for preparing grating and grating prepared by methodAfter metal film layers, silicon oxide and other etching barrier layers which are commonly adopted in the prior art are omitted, the parameter requirements of the grating can be met, the preparation process of the titanium dioxide grating is simplified, and the cost is reduced; in addition, as can be seen from fig. 7, when the imprinting adhesive layer is thin, a good mask effect is difficult to play, the shoulder of the imprinting adhesive is not sufficiently protected during the etching process, the morphology of the formed titanium dioxide grating is affected, and the thickness ratio of the imprinting adhesive layer to the titanium dioxide film layer needs to be within the range of 2 to 20 so as to achieve the mask etching effect; meanwhile, as can be seen from fig. 8, when the proportion of hydrogen bromide as a protective gas in the etching process is high, the etching rate of the titanium dioxide film is low, as shown in fig. 8, only 19nm is etched, the etching efficiency is low, and the popularization and the utilization are not facilitated; when the hydrogen bromide ratio of the protective gas in the etching process is too low, the protective gas can not sufficiently protect the side wall of the titanium dioxide grating, so that the inclination angle of the side wall is reduced. It can also be seen from FIGS. 9 and 10 that HBr and CF are adjusted 4 In a flow rate and ratio of 2 After the etched etching rate/the etched etching rate of the imprint resist/is more than 1, the etching rate of the imprint resist is too high, so that the shoulder protection of the grating is insufficient or even collapses in the etching process, and the appearance of the titanium dioxide grating is influenced.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, and not to limit the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Claims (10)
1. A method for preparing a titanium dioxide grating is characterized by comprising the following steps:
providing a substrate and a master plate with a titanium dioxide grating pattern;
sequentially forming a titanium dioxide film layer and an imprinting adhesive layer on the substrate, wherein the thickness of the imprinting adhesive layer is not less than 200nm;
transferring the pattern on the master mask to the titanium dioxide film layer by utilizing the processes of imprinting and etching to form a titanium dioxide grating;
wherein, the titanium dioxide film layer and the impression glue layer are not provided with an etching barrier layer; the aspect ratio of the titanium dioxide grating is 1/6 to 1/2; the aspect ratio is the ratio of the grating height to the grating width of any grating unit in the titanium dioxide grating.
2. The method for preparing the titanium dioxide grating as claimed in claim 1, wherein the thickness of the imprinting glue layer is 2 to 20 times of the thickness of the titanium dioxide film layer.
3. The method according to claim 1, wherein the processing gas in the etching process includes an etching gas for etching titanium dioxide and a protective gas for preventing the sidewalls of the grating units of the titanium dioxide grating from being etched by the etching gas, and the protective gas is hydrogen halide; and the ratio of the etching rate of the etching gas to the titanium dioxide film layer to the etching rate of the etching gas to the imprinting glue layer is not less than 1.
4. The method of claim 3, wherein the etching process is a dry etching process, and the dry etching process comprises:
adjusting the technological parameters of the dry etching process according to the longitudinal width ratio of the titanium dioxide grating to be obtained; and enabling the ratio of the etching rate of the etching gas to the titanium dioxide film layer to the etching rate of the etching gas to the imprinting glue layer to be not less than 1.
5. The method according to claim 4, wherein the process parameters include a ratio of the hydrogen halide in the etching gas, a gas flow rate of the hydrogen halide, a pressure in a chamber in which the dry etching process is performed, a temperature in the chamber in which the dry etching process is performed, and a source power used by a device in which the dry etching process is performed.
6. The method for manufacturing a titanium dioxide grating according to claim 5, wherein the ratio of the etching gas to the hydrogen halide is 1 to 3; and/or
The gas flow of the etching gas is 20 to 300SCCM; the gas flow of the hydrogen halide is 50 to 300SCCM; and/or
The pressure in the cavity for carrying out the dry etching process is 5 to 100mTorr; and/or
The temperature in a cavity for carrying out the dry etching process is 20 to 100 ℃; and/or
The source power adopted by the equipment for carrying out the dry etching process is 100 to 500w.
7. The method for manufacturing a titanium dioxide grating according to claim 4, wherein the etching gas is one or more selected from a group consisting of a fluorocarbon gas, a nitrogen-fluorine gas, and a sulfur-fluorine gas; and/or
The hydrogen halide is selected from one or more of hydrogen bromide, hydrogen chloride and hydrogen fluoride.
8. The method for manufacturing a titanium dioxide grating according to claim 1, further comprising, after the forming of the titanium dioxide grating: removing the residual imprinting glue layer;
removing the remaining imprint glue layer, including:
and utilizing a dry photoresist removing process and/or a wet photoresist removing process to remove the residual imprinting glue layer.
9. The method for manufacturing a titanium dioxide grating according to claim 1, wherein the titanium dioxide film layer is deposited on the substrate by a thin film process; the film process is selected from one or more of ALD technology, magnetron sputtering, electron beam evaporation, chemical vapor deposition and sol-gel method; and/or
The imprinting glue layer is formed on the titanium dioxide film layer by one or more of a slit coating process, a spray coating process, a spin coating process and a roll-to-roll coating process.
10. A titanium dioxide grating, characterized in that the grating is prepared by the method for preparing a titanium dioxide grating as defined in any one of claims 1 to 9.
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| US20050074697A1 (en) * | 2003-10-04 | 2005-04-07 | Massimo De Vittorio | Method for fabricating masters for imprint lithography and related imprint process |
| KR20180060585A (en) * | 2016-11-29 | 2018-06-07 | 한국과학기술원 | Method for forming nano patterns, method for preparing light emitting device and light emitting device prepared by the same |
| CN109795975A (en) * | 2018-12-28 | 2019-05-24 | 南京大学 | A kind of metal micro-/ nano linear array and preparation method thereof |
| CN111308597A (en) * | 2020-03-19 | 2020-06-19 | 华中科技大学 | Preparation method of submicron structure grating |
| US20210216009A1 (en) * | 2017-09-20 | 2021-07-15 | South University Of Science And University Of China | Method for preparing optical metasurfaces |
| CN114994817A (en) * | 2022-05-17 | 2022-09-02 | 北方夜视技术股份有限公司 | Preparation method of micro-nano grating |
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| US20050074697A1 (en) * | 2003-10-04 | 2005-04-07 | Massimo De Vittorio | Method for fabricating masters for imprint lithography and related imprint process |
| KR20180060585A (en) * | 2016-11-29 | 2018-06-07 | 한국과학기술원 | Method for forming nano patterns, method for preparing light emitting device and light emitting device prepared by the same |
| US20210216009A1 (en) * | 2017-09-20 | 2021-07-15 | South University Of Science And University Of China | Method for preparing optical metasurfaces |
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