CN109750253B - Preparation method of tilting structure - Google Patents

Preparation method of tilting structure Download PDF

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CN109750253B
CN109750253B CN201910021859.3A CN201910021859A CN109750253B CN 109750253 B CN109750253 B CN 109750253B CN 201910021859 A CN201910021859 A CN 201910021859A CN 109750253 B CN109750253 B CN 109750253B
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rectangle
photoresist
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CN109750253A (en
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不公告发明人
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Jiangsu runqi Project Management Co., Ltd
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Abstract

The invention relates to the field of micro-nano structure preparation, in particular to a preparation method of a tilting structure. The whole preparation process is simple and easy to operate, the preparation precision of the tilting structure is high, and the angle is easy to regulate and control.

Description

Preparation method of tilting structure
Technical Field
The invention belongs to the field of metal structure preparation, and particularly relates to a preparation method of a tilting structure.
Background
The first method is to use the traditional electron beam etching technology, multiple times of exposure and coating are needed, the preparation process is complicated, in addition, in the preparation process of the second layer or the third layer structure, the positioning is needed, the positioning process needs to be accurate, and otherwise, the prepared structure has larger errors. And the preparation time period of the electron beam exposure system is long, the metal layer is evaporated by the electron beam vacuum evaporation system, the spiral structure can be obtained only by evaporating the metal material for many times, and the process is complicated.
For the preparation of the tilting structure, two preparation methods are generally available, the first method is to use an etching technology, but the method needs to use an electron beam etching technology to perform three times of alignment, the field calibration is difficult, the time spent is long, the preparation process is complicated, the limiting factors in actual operation are more, and the prepared structure has larger errors; and secondly, by using an ion beam bombardment method, although the preparation precision is high, the equipment cost is high, the cost is high, and the processing efficiency is low.
Disclosure of Invention
In order to solve the problem of preparation of the tilting structure in the prior art, the invention provides a preparation method of the tilting structure.
A preparation method of a tilting structure comprises the following steps:
step 1: preparing a glass substrate, and coating two layers of photoresist on the substrate, wherein one layer is positive photoresist and the other layer is negative photoresist;
step 2: exposing the structural pattern by an electron beam, designing the pattern by using a pattern generator in a scanning electron microscope, and exposing a corresponding area;
and step 3: after the development and fixation treatment, evaporating the metal material;
and 4, step 4: lift-off stripping process is carried out by using stripping liquid.
And 5: the prepared structure is placed in a thermal field.
Further, the spinning method comprises the specific steps of spinning a layer of positive glue by 30nm by using a spinning machine, drying, then spinning a layer of negative glue by 90-100 nm, and drying.
Further, the specific process of exposing the structural pattern by the electron beam is as follows: the method comprises the steps of designing a pattern by using a pattern generator in a scanning electron microscope, wherein the designed pattern is an array structure arranged according to a rectangular period, each unit is composed of a first rectangle, a second rectangle, a third rectangle and a fourth region, the first rectangle is connected with the second rectangle, the second rectangle is connected with the third rectangle and is arranged in the middle of the rectangular period, and the region except the first rectangle, the second rectangle and the third rectangle in the period is the fourth region.
After the pattern is designed, the first rectangle, the third rectangle and the fourth area are exposed, and different exposure depths are adopted.
Further, the exposure depth of the first rectangle and the third rectangle exposed in step 3 is the sum of the thickness of the positive glue and the thickness of the negative glue, and the exposure depth of the fourth area is the thickness of the negative glue.
Further, the step 3 further comprises:
step 3 a: developing and fixing treatment and drying;
and step 3 b: vertically evaporating a layer of metal material;
and step 3 c: carrying out negative film development and fixation, and drying;
and step 3 d: vertically evaporating a layer of metal material;
furthermore, the thickness of the evaporated first layer of metal material in the step 3 is equal to that of the positive photoresist, and the thickness of the evaporated second layer of metal material is 30-40 nm.
Further, the step 4 specifically comprises the following steps:
step 4 a: carrying out lift-off process by using negative photoresist stripping liquid;
and 4 b: exposing the whole structure;
and 4 c: and then soaking the substrate by using positive photoresist developing solution.
Further, the metal material is gold, silver or copper.
Further, the rate of evaporating the metal material is
Figure BDA0001941035240000031
Further, the glass substrate is ITO glass.
The technical problem to be solved by the invention is realized by the following technical scheme:
compared with the prior art, the invention has the beneficial effects that:
(1) the preparation process of the three-dimensional tilting structure is simple and easy to operate, the field is firstly corrected once for the three-dimensional tilting structure, the nested structure is manufactured after electron beam evaporation is carried out twice, the nested structure is placed in a thermal field, and due to the fact that the photoresist of the inner structure and the metal material of the outer structure in the nested structure have different thermal expansion coefficients, when the temperature of the whole structure is changed, the photoresist and the metal material deform to different degrees, and when the temperature is adjusted to a certain degree, the outer metal material tilts to form the tilting structure. The temperature is further adjusted, the required three-dimensional tilting structure can be obtained, and the relation between the required tilting angle and the temperature of the thermal field is given in the embodiment;
(2) according to the embodiment of the application, the developing technology is utilized to act on the positive photoresist, and the positive photoresist is removed, so that the positive photoresist removing efficiency is greatly improved;
(3) the second exposure of the embodiment of the application does not need calibration, even does not need focusing on a scanning electron microscope, and only needs exposing the whole sample under an electron beam;
(4) the target structure and the metal structure to be removed are separated by the double-layer photoresist, so that the integrity of the target structure is ensured during single-layer photoresist removal, and unnecessary adhesion is avoided;
(5) according to the embodiment of the application, the wet lift-off process is only applied to the negative glue, so that the damage of the nested internal structure is avoided.
Drawings
Fig. 1 is a process flow of a method for manufacturing a tilted structure in embodiment 1 of the present application;
fig. 2 is a process flow of a method for manufacturing a tilted structure in embodiment 1 of the present application;
fig. 3 is a process flow of a method for manufacturing a tilted structure in embodiment 1 of the present application;
fig. 4 is a process flow of a method for manufacturing a tilted structure in embodiment 1 of the present application;
fig. 5 is a process flow of a method for manufacturing a tilted structure in embodiment 1 of the present application;
fig. 6 is a process flow of a method for manufacturing a tilted structure in embodiment 1 of the present application;
fig. 7 is a process flow of a method for manufacturing a tilted structure in example 1 of the present application;
fig. 8 is a process flow of a method for manufacturing a tilted structure in embodiment 1 of the present application;
fig. 9 is a process flow of a method for manufacturing a tilted structure in example 1 of the present application;
fig. 10 is a process flow of a method for manufacturing a tilted structure in example 1 of the present application;
FIG. 11 is a schematic diagram of the nested structure necessary for preparing the tilted structure in example 1 of the present application.
Fig. 12 is a process flow and a schematic structural diagram of a method for manufacturing a tilted structure in embodiments 2 and 3 of the present application.
FIG. 13 is a schematic diagram showing the relationship between the temperature of the thermal field and other parameters and the tilt angle in examples 2 and 3 of the present application.
Wherein, in fig. 1: 1. a first rectangle; 2. a second rectangle; 3. a third rectangle; 4. a fourth region; 100. a substrate; 101. positive glue; 102. negative glue; 103. a metallic material.
Detailed Description
In order to solve the problem of preparation of a chiral tilted structure in the prior art, the invention provides a preparation method of a tilted structure.
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example 1:
a preparation method of a tilting structure comprises the following steps:
firstly, an embedded structure is prepared by an electron beam etching technology and an electron beam vacuum evaporation technology, the internal structure of the embedded structure is photoresist, and a layer of metal is coated outside the embedded structure.
And then placing the prepared nested structure in a thermal field, and regulating and controlling the temperature of the thermal field to change the tilting angle of the required tilting structure.
This example shows a method for making a nested structure necessary for making a tilted structure, comprising the steps of:
step 1, preparing a glass substrate 100, and cleaning and drying the glass substrate;
specifically, the method comprises the following steps:
preparing an ITO glass substrate 100 with the thickness of 1.0mm and the length and width of 20.0mm plus 20.0mm, putting the prepared ITO glass into a washing solution for cleaning, carrying out ultrasonic treatment on the ITO glass for 15min by deionized water, carrying out ultrasonic treatment on the ITO glass for 15min by acetone, carrying out ultrasonic treatment on the ITO glass for 15min by alcohol, carrying out ultrasonic treatment on the ITO glass for 5min by deionized water, finally carrying out blow-drying by a nitrogen gun, and putting the ITO glass substrate into a nitrogen cabinet for later use.
Step 2, coating photoresist, and throwing two layers of photoresist on the surface of the substrate by using a photoresist throwing machine;
specifically, the method comprises the following steps:
the spin coating method specifically comprises the step of spinning a layer of positive photoresist 101 on a prepared glass substrate 100 by using a spin coating machine, wherein the positive photoresist 101 is positive photoresist 101 with a large thermal expansion coefficient, preferably PMMA. After drying, a layer of negative photoresist 102 is thrown by a photoresist spinner, as shown in FIG. 1, and dried, as shown in FIG. 2. The rotating speed of the rubber spinner is set to be 1000 rpm-6000 rpm, and the time is set to be 60 s. The temperature of the two drying processes is 150 ℃, the time is 3min, the hot plate is placed at a ventilation position in the ultra-clean room, the dust particles are few, the volatilization of organic matters is facilitated, and the temperature precision of the hot plate is +/-1 ℃.
The thickness of the positive throwing glue 101 is 30nm, and the thickness of the negative throwing glue 102 is 90-100 nm.
Step 3, exposing a structural pattern by an electron beam, designing the pattern by using a pattern generator in a scanning electron microscope, wherein the designed pattern is an array structure arranged according to a rectangular period, as shown in fig. 3, each unit consists of a first rectangle 1, a second rectangle 2, a third rectangle 3 and a fourth area 4, the first rectangle 1 is connected with the second rectangle 2, the second rectangle 2 is connected with the third rectangle 3 and is arranged at the middle position of the rectangular period, and the area except the first rectangle 1, the second rectangle 2 and the third rectangle 3 in the period is the fourth area 4;
after designing a graph, exposing a first rectangle 1, a third rectangle 3 and a fourth area 4, wherein the exposure depth of the first rectangle 1 and the third rectangle 3 is different from the exposure depth of the fourth area 4;
specifically, the method comprises the following steps:
as shown in fig. 4, the first rectangle 1 and the third rectangle 3 are exposed to a depth equal to the sum of the thicknesses of the positive glue 101 and the negative glue 102, and the fourth area 4 is exposed to a depth equal to the thickness of the negative glue 102. In the exposure process, multiple exposures can be adopted for the regions with deeper exposure depth, namely the first rectangle 1 and the third rectangle 3, so as to achieve the purpose of modifying the positive photoresist 101, the positive photoresist 101 in the exposure region becomes more soluble, after the development and fixation of the positive photoresist, the positive photoresist 101 in the exposure region is dissolved, the negative photoresist 102 in the exposure region becomes less soluble, and after the development and fixation of the negative photoresist, the negative photoresist 102 outside the exposure region is dissolved.
Step 4, positive photoresist developing and fixing, and treating with positive photoresist developing and fixing solution;
specifically, the method comprises the following steps:
at normal temperature, the substrate 100 after exposure is placed in a positive photoresistSoaking in developing solution for 60s, wherein the developing soaking time is controlled at constant time, the accuracy of the pattern and the exposure dose are linearly related under the determination of the developing time, and the exposure dose is 400 μ c/cm at 60s2(micro pools per square centimeter) is preferred; and (3) soaking and fixing the developed substrate in positive adhesive fixing solution for 60s, taking out after soaking, and drying by using nitrogen. As shown in fig. 5, after the positive photoresist development and fixing, since the first rectangle 1 and the third rectangle 3 are exposed to a depth equal to the sum of the thicknesses of the positive photoresist 101 and the negative photoresist 102 in step 3, the exposed photoresist is denatured, and the positive photoresist 101 in the first rectangle 1 and the third rectangle 3 becomes more easily dissolved, that is, the positive photoresist 101 in the first rectangle 1 and the third rectangle 3 is dissolved, and the negative photoresist 102 coated thereon is also removed at the same time.
Step 5, evaporating the metal material 103, and vertically evaporating the metal material 103 by using an electron beam vacuum evaporation coating instrument;
specifically, the method comprises the following steps:
controlling the vacuum degree of the electron beam vacuum evaporation coating machine to be not more than 3 x 10-6And (3) adjusting the angle of the sample stage to enable the plane of the sample stage to be vertical to the beam direction, wherein the thickness of the evaporated metal material 103 is equal to that of the positive photoresist 101, and the metal material 103 is gold, silver or copper, as shown in fig. 6. When the metal material 103 is evaporated by using the electron beam vacuum evaporation coater, the evaporation rate is controlled to
Figure BDA0001941035240000071
In a particular evaporation process, the initial evaporation rate is
Figure BDA0001941035240000072
The metal material 103 is better evaporated on the substrate 100 coated with the photoresist, and then the evaporation rate is adjusted to
Figure BDA0001941035240000073
Step 6, developing and fixing the negative glue, and processing the negative glue by using a negative glue developing and fixing solution;
specifically, the method comprises the following steps:
at normal temperature, the substrate 100 with the metal material 103 evaporated in the step 5 is placed into a negative photoresist developer for soaking and developing, the time for soaking and developing is controlled to be 60s, under the determination of the developing time, the graphic precision and the exposure dose are in a linear relation, and the exposure dose is 400 mu c/cm at 60s2(micro pools per square centimeter) is preferred; and (3) soaking and fixing the developed substrate in positive adhesive fixing solution for 60s, taking out after soaking, and drying by using nitrogen. After the negative film development and fixation, as shown in fig. 7, the negative film 102 at the second rectangle 2 is removed, and at the same time, the metal material 103 evaporated thereon is also removed.
Step 7, evaporating the metal material 103 again, and vertically evaporating the metal material 103 again by using an electron beam vacuum evaporation coating instrument;
specifically, the method comprises the following steps:
putting the substrate 100 subjected to the step 6 into an electron beam vacuum evaporation coating machine, and controlling the vacuum degree of the electron beam vacuum evaporation coating machine to be not more than 3 x 10-6torr, the metal material 103 is evaporated again, and the thickness of the evaporated metal material 103 is 30 to 40 nm. When the metal material 103 is evaporated by using the electron beam vacuum evaporation coater, the evaporation rate is controlled to
Figure BDA0001941035240000081
As shown in fig. 8, the surface of the whole structure is covered with a layer of metal material 103.
And 8, carrying out lift-off stripping process by using stripping liquid.
Specifically, the method comprises the following steps:
firstly, the substrate 100 on which the metal material 103 is deposited in the step 7 is soaked in the negative photoresist stripping solution to dissolve the negative photoresist 102, and the soaking time is at least 30 min. As shown in fig. 9, after the negative photoresist stripping solution treatment, the negative photoresist 102 at the fourth region 4 is dissolved, and the metal material 103 covered thereon is also removed.
Next, the whole structure is exposed by a scanning electron microscope without calibration, and after exposure, the photoresist is denatured, as shown in fig. 10, and the exposed thickness is the thickness of the positive photoresist 101.
Finally, the exposed substrate 100 is soaked in positive photoresist developing and fixing solution, and after the positive photoresist developing and fixing treatment, the positive photoresist 101 exposed outside is completely removed, and the whole structure only leaves the positive photoresist 101 embedded inside the metal material 103, as shown in fig. 11.
The step 8 of the preparation method of the embodiment of the application ensures that the positive glue 101 nested in the middle of the structure can not be dissolved, and ensures that the external positive glue 101 is completely dissolved, and even if the negative glue 102 is not completely peeled off when the negative glue stripping liquid is used, the positive glue 101 can be dissolved to ensure that the surrounding substances can be stripped off when the positive glue development and fixation are carried out.
The embodiment can accurately obtain the nested structure, and the surrounding of the nested structure is free from any impurity to influence the performance of the nested structure.
Example 2
In the embodiment, the nested structure prepared in the embodiment 1 is placed in a thermal field to prepare the tilted structure, and because the internal structure photoresist and the external structure metal material in the nested structure have different thermal expansion coefficients, the photoresist and the metal material deform to different degrees when the temperature of the whole structure is changed, and when the temperature is adjusted to a certain degree, the external metal material tilts to form the tilted structure. As shown in fig. 12, placing the nested structure in a thermal field will result in a tilted structure with a tilt angle θ corresponding to the temperature.
The outer structure of the nested structure prepared in example 1 is a metal material 103, the metal material 103 is gold, silver or copper, the inner structure is photoresist, and the positive photoresist is positive photoresist with a large thermal expansion coefficient.
The thermal expansion coefficient of the metal material 103 is much smaller than that of the photoresist, so that when the temperature of the thermal field is raised, the deformation of the external metal material 103 is larger than that of the positive photoresist 101, and at this time, the metal material 103 coated on the external part is tilted, and the whole structure forms a three-dimensional tilting structure.
The tilting angle of the tilting structure is changed by regulating and controlling the thermal field, the temperature of the thermal field is changed, and the calculation of the tilting angle is as follows:
as shown in fig. 13, the thermal expansion coefficient α of the metal material 103 is known1Coefficient of thermal expansion α of the positive paste 1012
h is the thickness of the metal material 103 and l is the length of the positive glue 101
The amount of deformation of the metallic material 103 can be calculated: l1=ΔT*l*α1
Deformation amount of the positive glue 101: l2=ΔT*l*α2
Thickness of expanded metal material 103: h ═ Δ T ═ H ^ α1+h
If the diagram theta is 90-gamma,
Figure BDA0001941035240000101
Figure BDA0001941035240000102
thus, the tilt angle
Figure BDA0001941035240000103
Example 3
In this embodiment, the nested structure prepared in the above embodiment 1 is placed in a thermal field to prepare a tilted structure.
The tilting angle of the tilting structure is changed by regulating and controlling the thermal field, the temperature of the thermal field is changed, and the calculation of the tilting angle is as follows:
as shown in FIG. 13, the thermal expansion coefficient α of PMMA is knownpAt 85um/m DEG C, the coefficient of thermal expansion of Au being alphaAuA thermal expansion coefficient alpha of Ag of 14.2um/m DEG CAgAt 19.5um/m x ℃.
h is the thickness of Au and l is the length of PMMA.
The deformation of Au can be calculated: lAu=ΔT*l*αAu
Amount of deformation of PMMA: lP=ΔT*l*αP
Thickness of Au after swelling: h ═ΔT*h*αAu+h
If the diagram theta is 90-gamma,
Figure BDA0001941035240000104
Figure BDA0001941035240000105
thus, the tilt angle
Figure BDA0001941035240000111
In summary, the tilting angle of the tilting structure can be calculated according to the above formula, and conversely, to obtain a tilting structure with a certain angle, the structure can also be designed according to the above formula.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.

Claims (5)

1. The preparation method of the tilting structure is characterized by comprising the following steps:
step 1: preparing a glass substrate (100), coating two layers of photoresist on the substrate (100), wherein one layer is positive photoresist (101) and the other layer is negative photoresist (102);
step 2: exposing the structural pattern by an electron beam, designing the pattern by using a pattern generator in a scanning electron microscope, and exposing a corresponding area; the method specifically comprises the following steps:
designing a pattern by using a pattern generator in a scanning electron microscope, wherein the designed pattern is an array structure arranged according to a rectangular period, and each unit consists of a first rectangle, a second rectangle, a third rectangle and a fourth area; the first rectangle is connected with the second rectangle, the second rectangle is connected with the third rectangle, and the first rectangle, the second rectangle and the third rectangle are arranged in the middle of the rectangle period; the region excluding the first rectangle, the second rectangle and the third rectangle in the period is the fourth region;
exposing the first rectangle, the third rectangle and the fourth region with different exposure depths; wherein the exposure depth of the first rectangle and the third rectangle is the thickness of the sum of the thickness of the positive glue (101) and the thickness of the negative glue (102), and the exposure depth of the fourth area is the thickness of the negative glue (102);
and step 3: after the development and fixation treatment, evaporating the metal material (103); the method specifically comprises the following steps:
step 3 a: developing and fixing treatment and drying;
and step 3 b: vertically evaporating a layer of metal material (103); the evaporation thickness is the thickness of the positive photoresist (101);
and step 3 c: carrying out negative film development and fixation, and drying;
and step 3 d: then vertically evaporating a layer of metal material (103); the evaporation thickness is 30-40 nm;
the thermal expansion coefficient of the metal material (103) is far smaller than that of the photoresist;
and 4, step 4: carrying out lift-off stripping process by using stripping liquid; the method specifically comprises the following steps:
step 4 a: carrying out lift-off process by using negative photoresist stripping liquid;
and 4 b: exposing the whole structure;
and 4 c: then soaking the substrate by using positive photoresist developing solution;
and 5: the prepared structure is placed in a thermal field.
2. The method for preparing the tilted structure according to claim 1, wherein the step of coating two layers of photoresist comprises the steps of throwing a layer of positive photoresist (101) by 30nm by using a spin coater, drying, then throwing a layer of negative photoresist (102) by 90-100 nm, and drying.
3. The method for manufacturing a tilted structure according to claim 1, wherein the metal material (103) is gold, silver or copper.
4. The method for producing a tilted structure according to claim 3, wherein the rate of evaporating the metal material (103) is such that
Figure FDA0002625438180000021
5. The method for manufacturing the tilted structure according to claim 4, wherein the glass substrate (100) is ITO glass.
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