CN108255013B - Processing method for increasing occupied width ratio of photoresist grating mask - Google Patents
Processing method for increasing occupied width ratio of photoresist grating mask Download PDFInfo
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- CN108255013B CN108255013B CN201810156245.1A CN201810156245A CN108255013B CN 108255013 B CN108255013 B CN 108255013B CN 201810156245 A CN201810156245 A CN 201810156245A CN 108255013 B CN108255013 B CN 108255013B
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
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Abstract
The invention is suitable for the technical field of grating processing, and provides a processing method for increasing the ratio of the occupied width of a photoresist grating mask, which comprises the following steps: placing a substrate with a photoresist grating mask on a heating platform; covering a PDMS gasket on the surface of the grating mask, and preheating; rolling the PDMS gasket in a one-way manner towards the extending direction of the grating strip by using a round bar until the PDMS gasket is completely contacted with the grating mask; sequentially covering a tissue sheet and a glass substrate on the PDMS gasket; applying a load to the glass substrate from top to bottom to heat the grating substrate; cooling the grating to below the glass transition temperature of the photoresist, and sequentially removing the load, the glass substrate and the thin paper sheet; and uncovering one end of the PDMS gasket, and slowly uncovering the whole PDMS gasket to obtain the photoresist grating mask with the increased aspect ratio. The grating mask obtained by the processing method has the advantages that the occupied width ratio of the grating mask is obviously increased, the thickness of the grating mask lines is uniform, the surfaces of the grating mask lines are smooth, and the side walls are steep.
Description
Technical Field
The invention belongs to the technical field of grating micro-nano processing, and provides a processing method for increasing the occupied width ratio of a photoresist grating mask.
Background
The X-ray self-supporting blazed transmission grating has the advantages of high efficiency and high resolution of broadband, and has great application requirements in the fields of inertial confinement fusion plasma diagnosis, astronomical physics, X-ray phase contrast imaging and the like. Holographic lithography-monocrystalline silicon anisotropic wet etching is an important method for manufacturing an X-ray self-supporting blazed transmission grating. The large occupied width ratio of the grating mask can obviously increase the process latitude of the anisotropic wet etching of the monocrystalline silicon and improve the success rate of grating manufacture. However, since the aspect ratio of the grating mask obtained by the holographic lithography technology is small, the aspect ratio of the grating mask must be increased after the holographic lithography.
At present, two methods for increasing the ratio of the occupied width of a grating mask after holographic lithography are available:
the method is characterized in that the Lift-off process method is based on the principle that the aspect ratio of a mask pattern is reversed, and a photoresist grating with a small aspect ratio is converted into a metal grating with a large aspect ratio. However, the photoresist grating lines are required to be of a structure with a wide top and a narrow bottom, which has very high requirements on the process conditions of the previous holographic lithography. And the Lift-off method relates to a coating process, needs expensive coating equipment and has higher cost.
The other is an inclined coating method, which is to realize the increase of the ratio of the occupied width by utilizing the deposition and widening of metal atoms on the top of the photoresist lines. The metal film is obliquely attached to the top of the grating line, so that collapse is easily formed under the self gravity and external interference, and mask defects are caused. In order to avoid the collapse of the metal film, the process conditions of the inclined coating film and the storage conditions of the sample need to be strictly controlled. In addition, the method needs expensive coating equipment and is high in cost.
Disclosure of Invention
The embodiment of the invention provides a processing method for increasing the ratio of the occupied width of a photoresist grating mask, and aims to solve the problems of high requirements on process conditions and high cost in the existing method.
The invention is realized in this way, a processing method for increasing the ratio of the occupied width of a photoresist grating mask, which comprises the following steps:
s1, placing the substrate with the photoresist grating mask on a heating platform;
s2, covering a PDMS gasket on the surface of the grating mask, and preheating, wherein the preheating temperature is lower than the glass transition temperature of the photoresist;
s3, rolling the PDMS gasket in a one-way mode towards the extending direction of the grating strip by using a round bar until the PDMS gasket is completely contacted with the grating mask;
s4, sequentially covering a tissue sheet and a glass substrate on the PDMS gasket;
s5, applying a load to the glass substrate from top to bottom, heating the grating substrate to a temperature above the glass transition temperature of the photoresist;
s6, cooling the grating to be below the glass transition temperature of the photoresist, and sequentially unloading the load, the glass substrate and the thin paper sheet;
and S7, uncovering one end of the PDMS gasket, and slowly uncovering the whole PDMS gasket to obtain the photoresist grating mask with the increased aspect ratio.
Further, the heating temperature in step S5 is: the heating time is 20 to 80 minutes at the temperature of between 140 and 180 ℃, and the corresponding applied load is 50 to 500 kPa.
Further, the preheating condition in step S2 is: the heating temperature is 80 ℃, and the preheating time is 5 minutes.
Further, the manufacturing process of the PDMS gasket includes the following steps:
s21, mixing the prepolymer SYLGARD 184silicon ELASTOMER and CURING AGENT SYLGARD 184CURING AGENT in a volume ratio of 10:1 to form a viscous mixture;
s22, removing bubbles in the viscous mixed liquid;
s23, directly pouring the viscous mixed solution onto a flat and smooth substrate, and naturally flattening the mixed solution under the wetting action until the substrate is completely covered;
s24, placing the substrate with the surface completely covered with the mixed liquid on a heating table for heating and curing;
and S25, uncovering the cured PDMS gasket from one end of the substrate, and slowly and wholly uncovering to obtain the PDMS gasket.
Further, the curing conditions in step S24 are as follows:
the substrate with the surface completely covered with the mixed solution was placed on a 75 ℃ heating stage, heated for 4 hours, and then the heating stage was heated to 180 ℃ for 1 hour.
Further, the removing of the air bubbles in the viscous mixed liquid in the step S24 includes the following steps:
standing at normal pressure and room temperature for more than 1 hour or placing in a vacuum oven with 133Pa at room temperature for more than 20 minutes.
Further, the photoresist used is subjected to heating and pressing to generate unrecoverable deformation.
The processing method for increasing the occupied width ratio of the photoresist grating mask provided by the embodiment of the invention has the following beneficial effects:
1. when the occupied width ratio of the grating mask obtained by the processing method is obviously increased, the thickness of the grating mask lines is uniform, the surfaces of the grating mask lines are smooth, and the side walls are steep;
2. the whole processing process is simple to operate, the requirement on process conditions is low, equipment is simple, and the cost is low;
3. the thin paper sheet is arranged between the glass substrate and the PDMS gasket, so that the glass substrate and the PDMS gasket are prevented from being adhered together under heating and pressurizing to cause demoulding difficulty, and the problem of collapse of grating mask lines caused by too large demoulding force is avoided.
4. The round bar is used for rolling the PDMS gasket towards the extension direction of the grating strip in a one-way mode, so that air bubbles can be completely expelled to enable the PDMS gasket to be in complete contact with the grating mask, and the problem of mask quality caused by uneven load conduction is solved.
Drawings
FIG. 1 is a flowchart of a processing method for increasing the aspect ratio of a photoresist grating mask according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a substrate with a photoresist grating mask placed on a heated platen according to an embodiment of the present invention;
FIG. 3 is a schematic structural diagram of a PDMS gasket disposed on a grating mask according to an embodiment of the present invention;
FIG. 4 is a schematic structural diagram of a cylindrical bar single-direction rolled PDMS gasket according to an embodiment of the present invention;
FIG. 5 is a schematic structural view of a lidded tissue sheet and a glass substrate according to an embodiment of the present invention;
FIG. 6 is a schematic view of a structure for applying a load to a glass substrate according to an embodiment of the present invention;
FIG. 7 is a schematic structural view of a PDMS gasket according to an embodiment of the present invention;
fig. 8 is a scanning electron microscope image of a processed grating mask, in which a PDMS spacer provided in an embodiment of the present invention is not in complete contact with the grating mask;
FIG. 9 is a scanning electron microscope image of an original raster mask provided by an embodiment of the present invention;
FIG. 10 is a scanning electron microscope image of a processed reticle mask provided by an embodiment of the present invention;
fig. 11 is a scanning electron microscope image of a grating mask formed by incomplete curing processing of a PDMS gasket according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Fig. 1 is a flowchart of a processing method for increasing an aspect ratio of a photoresist grating mask according to an embodiment of the present invention, where the method includes the following steps:
s1, placing the substrate with the photoresist grating mask on a heating platform;
as shown in FIG. 2, 1 is a substrate, 2 is a photoresist grating mask, 3 is a heating platform, the bottom surface of the substrate is in contact with the heating platform, the grating is placed upwards, and the heating platform is a KW-4AH-350 type baking machine of Camet.
S2, covering a PDMS gasket on the surface of the grating mask, and preheating, wherein the preheating temperature is lower than the glass transition temperature of the photoresist;
as shown in fig. 3, 4 is a PDMS gasket, and the size of the gasket is exactly or slightly smaller than that of the grating mask substrate, in the embodiment of the present invention, the glass transition temperature of the photoresist refers to a temperature corresponding to a transition of the photoresist from a solid state to a viscous state, the photoresist is in the solid state when the glass transition temperature of the photoresist is lower than, and the photoresist is in the viscous state when the glass transition temperature of the photoresist is slightly higher than;
the photoresist adopted by the embodiment of the invention is RZJ-390PG of Suzhou Rehong electronic chemicals, and the glass transition temperature of the photoresist is higher than 120 ℃, so that the temperature of the heating table is set to be 80 ℃, and the photoresist is preheated for 5 minutes after reaching 80 ℃;
in the embodiment of the invention, the surface of the grating mask is preheated after being covered with the PDMS gasket, and the function of the PDMS gasket is to heat and release sealed gas, so that the PDMS gasket is better attached to the grating mask.
S3, rolling the PDMS gasket in a one-way mode towards the extending direction of the grating strip by using a round bar until the PDMS gasket is completely contacted with the grating mask;
as shown in fig. 4, 5 is a round bar, in the embodiment of the present invention, in order to make the PDMS pad completely contact with the grating mask, that is, in order to make no bubble exist on the contact surface of the PDMS pad and the grating mask, the round bar is unidirectionally rolled on the PDMS pad in the extending direction of the grating strip until all the bubbles are expelled, and since the PDMS is a soft transparent elastomer, it can be visually detected whether the PDMS pad completely contacts with the grating mask.
It is known from a lot of experiments that when bubbles exist between the contact surfaces of the PDMS gasket and the grating mask, and when the step S5 is performed to heat and pressurize the grating mask, due to the blocking of the bubbles, the applied load is not applied to the grating mask, the grating naturally deforms under the heating condition, the surface of the grating mask line is not flat, the sidewall is not steep, and the entire line has a nodular phenomenon, as shown in fig. 8.
S4, sequentially covering a tissue sheet and a glass substrate on the PDMS gasket;
as shown in fig. 5, 6 is a paper sheet, 7 is a glass substrate, the paper sheet is used for isolating the PDMS gasket from the glass substrate, and preventing the PDMS gasket and the glass substrate from being stuck together under heat and pressure, which causes difficulty in demolding, and a general mirror wiping paper is selected, and the glass substrate can bear the applied load as long as the surface is flat, such as a common window glass. In the present examples, the selected thickness ranges for the tissue sheet are: less than 0.2 mm.
The lens wiping paper is a new star lens wiping paper produced by Hangzhou special paper industry Co.
S5, applying a load to the glass substrate from top to bottom, heating the grating substrate to a temperature above the glass transition temperature of the photoresist;
the heating temperature is too low, the photoresist is in a solid state, the aspect ratio of the grating mask is difficult to increase even if the photoresist is pressurized, the heating temperature is too high, the photoresist grating mask is melted, and the deformation is uncontrollable. The heating temperature can be determined by a contrast experiment on the basis of the reference photoresist specification, for the model of RZJ-390PG photoresist, the heating temperature is between 140 ℃ and 180 ℃, the photoresist is in a viscous flow state, and controllable deformation can be generated by pressurization;
as shown in fig. 6, when the heating temperature is 140-180 ℃, the load is too small to achieve the effect of increasing the aspect ratio of the grating mask, and the load is too large, which may cause the grating mask to be flattened or adjacent grating lines to contact. A large number of experiments prove that when the heating temperature is 140-180 ℃, the applied load is 50-500 kPa. The load can be applied by stacking standard lead blocks, and the heating time is controlled to be 20-80 minutes.
S6, cooling the grating to be below the glass transition temperature of the photoresist, and sequentially unloading the load, the glass substrate and the thin paper sheet;
in the embodiment of the present invention, after the grating mask is heated to the glass transition temperature or higher in step S5, the aspect ratio of the grating mask is increased under the action of the load, and therefore, to maintain the increased aspect ratio of the grating mask, the temperature of the grating mask is first lowered to make the temperature of the photoresist grating mask lower than the glass transition temperature, and then the load is removed, so that the aspect ratio of the grating mask is maintained at the increased aspect ratio.
And S7, uncovering one end of the PDMS gasket, and slowly uncovering the whole PDMS gasket to obtain the photoresist grating mask with the increased aspect ratio.
As shown in fig. 7, since the PDMS pad is a soft elastomer, the entire PDMS pad can be slowly removed by removing one end of the PDMS pad, so that the PDMS pad is completely separated from the grating mask, and the problem of collapse of the grating mask lines due to too large release force does not occur;
fig. 9 is a scanning electron microscope image of an original grating mask, fig. 10 is a scanning electron microscope image of a processed grating mask, and comparing fig. 9 and fig. 10, it can be known that the grating mask obtained by the above processing has an obviously increased aspect ratio, and simultaneously, the grating mask has uniform line thickness, flat surface and steep side wall.
The processing method for increasing the occupied width ratio of the photoresist grating mask provided by the embodiment of the invention has the following beneficial effects:
1. when the occupied width ratio of the grating mask obtained by the processing method is obviously increased, the thickness of the grating mask lines is uniform, the surfaces of the grating mask lines are smooth, and the side walls are steep;
2. the whole processing process is simple to operate, the requirement on process conditions is low, equipment is simple, and the cost is low;
3. the thin paper sheet is arranged between the glass substrate and the PDMS gasket, so that the glass substrate and the PDMS gasket are prevented from being adhered together under heating and pressurizing to cause demoulding difficulty, and the problem of collapse of grating mask lines caused by too large demoulding force is avoided.
4. The round bar is used for rolling the PDMS gasket towards the extension direction of the grating strip in a one-way mode, so that air bubbles can be completely expelled to enable the PDMS gasket to be in complete contact with the grating mask, and the problem of mask quality caused by uneven load conduction is solved.
In the embodiment of the invention, the manufacturing process of the PDMS gasket comprises the following steps:
s21, mixing the prepolymer (SYLGARD 184SILICONE ELASTOMER) and the CURING AGENT (SYLGARD 184CURING AGENT) at a volume ratio of 10:1 to obtain a viscous mixture;
s22, removing bubbles in the viscous mixed liquid;
in the embodiment of the present invention, there are two methods for removing bubbles in the mixed solution: standing at normal pressure and room temperature for more than 1 hour or placing in a 133Pa vacuum oven at room temperature for more than 20 minutes to remove bubbles in the mixed solution;
s23, directly pouring the viscous mixed liquid on the surface of a substrate, naturally flattening the mixed liquid under the wetting action until the mixed liquid completely covers the substrate, wherein the substrate is a glass substrate or a silicon substrate with a smooth and flat surface;
s24, placing the substrate with the surface completely covered with the mixed liquid on a heating table for heating and solidifying.
In the embodiment of the present invention, the curing conditions of the existing PDMS gasket are recommended in the specification: the substrate with the surface completely covered with the mixed solution was placed on a 75 ℃ heating stage and heated for 1.5 hours. The grating mask obtained based on the existing PDMS gasket processing has the problems of uneven line surface and not steep sidewall of the grating mask, as shown in fig. 11. A large number of experiments find that the curing of the PDMS gasket is incomplete, when the photoresist is heated to 140-180 ℃, the PDMS gasket is still cured, and the strength of the PDMS gasket is not enough to press the surface of the grating mask to be flat. Therefore, through a series of experimental searches, the optimal curing conditions are as follows: the substrate with the surface completely covered with the mixed solution is placed on a heating table at 75 ℃ and heated for 4 hours, and then the heating table is heated to 180 ℃ and heated for 1 hour.
In order to avoid the warpage of the PDMS gasket caused by the overlarge stress caused by sudden heating from room temperature to high temperature in the curing process, the substrate with the surface completely covered with the mixed solution is pre-cured at a lower temperature, then the temperature of the heating table is raised to the highest temperature value of 180 ℃ for heating the photoresist, and the substrate is fully cured at the temperature. Therefore, when the photoresist is heated to 140-180 ℃, the PDMS gasket can keep enough strength.
And S25, uncovering the cured PDMS gasket from one end of the substrate, and slowly and wholly uncovering to obtain the PDMS gasket.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (5)
1. A processing method for increasing the duty ratio of a photoresist grating mask is characterized by comprising the following steps:
s1, placing the substrate with the photoresist grating mask on a heating platform;
s2, covering a PDMS gasket on the surface of the grating mask, and preheating, wherein the preheating temperature is lower than the glass transition temperature of the photoresist;
s3, rolling the PDMS gasket in a one-way mode towards the extending direction of the grating strip by using a round bar until the PDMS gasket is completely contacted with the grating mask;
s4, sequentially covering a tissue sheet and a glass substrate on the PDMS gasket;
s5, applying a load to the glass substrate from top to bottom, heating the grating substrate to a temperature above the glass transition temperature of the photoresist;
s6, cooling the grating to be below the glass transition temperature of the photoresist, and sequentially unloading the load, the glass substrate and the thin paper sheet;
s7, uncovering one end of the PDMS gasket, and slowly uncovering the whole PDMS gasket to obtain the photoresist grating mask with the increased aspect ratio;
the heating temperature in step S5 is: the heating time is 20 to 80 minutes at the temperature of between 140 and 180 ℃, and the corresponding applied load is 50 to 500 kPa;
the preheating conditions in step S2 are: the heating temperature is 80 ℃, and the preheating time is 5 minutes.
2. The processing method for increasing the aspect ratio of a photoresist grating mask according to claim 1, wherein the process for manufacturing the PDMS gasket comprises the following steps:
s21, mixing the prepolymer SYLGARD 184silicon ELASTOMER and CURING AGENT SYLGARD 184CURING AGENT in a volume ratio of 10:1 to form a viscous mixture;
s22, removing bubbles in the viscous mixed liquid;
s23, directly pouring the viscous mixed solution onto a flat and smooth substrate, and naturally flattening the mixed solution under the wetting action until the substrate is completely covered;
s24, placing the substrate with the surface completely covered with the mixed liquid on a heating table for heating and curing;
and S25, uncovering the cured PDMS gasket from one end of the substrate, and slowly and wholly uncovering to obtain the PDMS gasket.
3. The processing method for increasing the aspect ratio of a photoresist grating mask as claimed in claim 2, wherein the curing conditions in step S24 are as follows:
the substrate with the surface completely covered with the mixed solution was placed on a 75 ℃ heating stage, heated for 4 hours, and then the heating stage was heated to 180 ℃ for 1 hour.
4. The method as claimed in claim 2, wherein the step S24 of removing the bubbles in the viscous mixture comprises the following steps:
standing at normal pressure and room temperature for more than 1 hour or placing in a vacuum oven with 133Pa at room temperature for more than 20 minutes.
5. The method of claim 1, wherein the photoresist is heated and pressed to cause an unrecoverable deformation.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1755472A (en) * | 2004-10-01 | 2006-04-05 | 三星电子株式会社 | The manufacture method of LCD and with therein mask |
| WO2009142787A2 (en) * | 2008-02-18 | 2009-11-26 | Board Of Regents, The University Of Texas System | Photovoltaic devices based on nanostructured polymer films molded from porous template |
| CN102483337A (en) * | 2009-07-16 | 2012-05-30 | 哈米德瑞萨·埃洛莫哈迈德 | Optical fibre sensor and methods of manufacture |
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| KR100928057B1 (en) * | 2008-03-27 | 2009-11-23 | 한국표준과학연구원 | Super water-repellent surface modification method using ultrafast laser |
| CN102981198A (en) * | 2012-12-12 | 2013-03-20 | 中国科学院长春光学精密机械与物理研究所 | Wet etching method of echelle grating in single-crystal silicon |
| CN105487151A (en) * | 2016-01-22 | 2016-04-13 | 武汉理工大学 | Grating preparation method through pattern transfer based on nano-imprint |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1755472A (en) * | 2004-10-01 | 2006-04-05 | 三星电子株式会社 | The manufacture method of LCD and with therein mask |
| WO2009142787A2 (en) * | 2008-02-18 | 2009-11-26 | Board Of Regents, The University Of Texas System | Photovoltaic devices based on nanostructured polymer films molded from porous template |
| CN102483337A (en) * | 2009-07-16 | 2012-05-30 | 哈米德瑞萨·埃洛莫哈迈德 | Optical fibre sensor and methods of manufacture |
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