CN113075868A - Photoresist patterning method and double-layer photoresist stripping method - Google Patents
Photoresist patterning method and double-layer photoresist stripping method Download PDFInfo
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- CN113075868A CN113075868A CN202010010237.3A CN202010010237A CN113075868A CN 113075868 A CN113075868 A CN 113075868A CN 202010010237 A CN202010010237 A CN 202010010237A CN 113075868 A CN113075868 A CN 113075868A
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- G—PHYSICS
- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/322—Aqueous alkaline compositions
-
- G—PHYSICS
- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
The invention discloses a photoresist patterning method and a double-layer photoresist stripping method; the method comprises the following steps: sequentially forming a first photoresist layer and a second photoresist layer on a substrate; exposing the first photoresist layer and the second photoresist layer simultaneously by using a mask; carrying out positive development on the exposed first photoresist layer and the exposed second photoresist layer by using a positive developing solution to form a first opening and a second opening which are equal in width in the first photoresist layer and the second photoresist layer respectively; and carrying out negative development on the first photoresist layer by adopting a negative developing solution, and increasing the width of the first opening to enable the width of the first opening to be larger than that of the second opening. The invention adopts the negative developing process of the positive photoresist, and utilizes the characteristic that the positive photoresist in the non-exposure area is dissolved in the negative developing solution, so that the shape of the pattern can be accurately controlled to reach the inverted T-shaped pattern, the secondary exposure of the required pattern is avoided, and the high resolution of the pattern is ensured.
Description
Technical Field
The invention relates to the field of semiconductor integrated circuit manufacturing, in particular to a photoresist patterning method and a double-layer photoresist stripping method.
Background
In a semiconductor manufacturing process, metal patterns are usually used for manufacturing leads and electrodes of a device, and the metal patterns are usually formed by a method of first performing photolithography and then performing wet or dry etching, but some metals are difficult to etch by wet or dry etching, and chemical substances required for etching the metal patterns have an etching effect on other parts of the semiconductor device, so that the metal patterns are usually manufactured by a lift-off process.
The traditional double-layer adhesive stripping process adopts an inverted T-shaped structure with a narrow top and a wide bottom, so that the metal stripping difficulty is reduced, and the stripping efficiency is improved; however, the preparation process is complex, and usually requires an additional exposure step or an additional developing solution and developing step to increase the developing rate of the underlying photoresist, and the preparation process is complex and costly. In addition, the photolithography process in the current practical production utilizes the positive development technology to pattern the positive photoresist, and under the condition of adopting the two-time positive development photolithography process, the array pattern can be subjected to two exposures, which can seriously affect the pattern effect and can not meet the production requirement.
Disclosure of Invention
In order to accurately control the shape of a graph to reach an inverted T-shaped graph, avoid secondary exposure of a required pattern and ensure high resolution of the pattern, the invention provides a photoresist patterning method and a double-layer photoresist stripping method.
The technical contents for solving the technical problems are as follows:
a method of patterning a photoresist, the method comprising:
sequentially forming a first photoresist layer and a second photoresist layer on a substrate;
exposing the first photoresist layer and the second photoresist layer simultaneously by using a mask;
carrying out positive development on the exposed first photoresist layer and the exposed second photoresist layer by using a positive developing solution to form a first opening and a second opening which are equal in width in the first photoresist layer and the second photoresist layer respectively;
and carrying out negative development on the first photoresist layer by adopting a negative developing solution, and increasing the width of the first opening to enable the width of the first opening to be larger than that of the second opening.
Further, the first photoresist layer and the second photoresist layer are both positive photoresists.
Further, the positive developing solution is tetramethylammonium hydroxide or tetraethylammonium hydroxide.
Further, the negative developing solution is n-butyl acetate or methyl isobutyl carbinol.
Further, before the negative developing of the first photoresist layer with the negative developing solution, the method comprises the following steps: and curing the second photoresist layer.
In a further embodiment, the second photoresist layer comprises a photoacid generator and a phenolic resin, and the second photoresist layer is cured using hexamethylenetetramine.
Further, the dosage of hexamethylene tetramine is 10-15%, and the curing temperature is 150-170 ℃.
Further, the step of simultaneously exposing the first photoresist layer and the second photoresist layer by using a mask comprises: the focal length of the first photoresist layer and the second photoresist layer is-0.05 um and is between 20mj/cm2～25mj/cm2The exposure dose of (a) is irradiated.
A double-layer photoresist stripping method comprises the following steps:
forming a first patterned photoresist layer and a second patterned photoresist layer on a substrate by adopting the method of any scheme;
forming a layer metal film on a substrate;
and removing the first photoresist layer and the second photoresist layer.
Further, the thickness of the metal film is smaller than that of the first photoresist layer.
Further, the photoresist is stripped by one or more of N-methyl pyrrolidone, gamma-butyrolactone or ethyl lactate.
Further, the metal film is made of copper, gold, titanium, nickel, silver, platinum or chromium.
Compared with the prior art, the invention has the advantages that:
according to the invention, a negative developing process of a positive photoresist is adopted, the positive photoresist used for the negative developing process is used as the bottom photoresist of the double-layer photoresist, and the characteristic that the positive photoresist in a non-exposure area is dissolved in a negative developing solution is utilized, so that the width of a first opening of a first photoresist layer is larger than the width of a second opening of a second photoresist layer, the shape of a pattern is accurately controlled to reach an inverted T-shaped pattern, secondary exposure to a required pattern is avoided, and the high resolution of the pattern is ensured; in addition, the patterning method can be used for accurately preparing the electrode or the lead of the semiconductor device, and the problem of complex process for preparing the metal pattern in the double-layer photoresist stripping process is solved.
Drawings
FIG. 1 is a flowchart showing steps of a resist patterning method according to embodiment 1 of the present invention;
FIG. 2 is a schematic view of a bilayer photoresist structure in example 1 of the present invention;
FIG. 3 is a schematic view of a bilayer resist exposure process in example 1 of the present invention;
FIG. 4 is a schematic structural view of a pattern obtained after the developing treatment in example 1 of the present invention;
FIG. 5 is a schematic view of a pattern structure obtained after the curing treatment in example 1 of the present invention;
FIG. 6 is a schematic view showing a structure of a pattern obtained after the negative development treatment in example 1 of the present invention;
FIG. 7 is a schematic structural view of the structure of FIG. 6 after a metal film is formed on the surface thereof in example 2 of the present invention;
FIG. 8 is a schematic diagram showing a structure of a pattern after photoresist is stripped in embodiment 2 of the present invention;
FIG. 9 is a flowchart illustrating a method for stripping bilayer resist according to embodiment 2 of the present invention.
In the figure: 200-a substrate; 201-a first photoresist layer; 202-a second photoresist layer; 203-first exposure area; 204-second exposure area; 205-a first opening; 206-a second opening; 207-mask plate; 208-curing the layer; 209-metal film.
Detailed Description
Embodiments of the present invention are described in detail below with reference to the attached drawing figures, examples of which are illustrated in the drawing figures.
It should be noted that, in this document, the positive developing solution refers to a developing solution used in a positive developing process, and the photoresist is insoluble in the positive developing solution before exposure, and is soluble in the positive developing solution after exposure, so that the exposed region is removed and the unexposed region is left. The negative developing solution is used for a negative developing process, the photoresist is dissolved in the negative developing solution before exposure, and is not dissolved in the negative developing solution after exposure, so that an exposed area is left, and an unexposed area is removed.
Example 1
As shown in fig. 1, an embodiment of the invention discloses a method for patterning a photoresist.
Spin-coating a photoresist on the surface of the substrate 200 to form a first photoresist layer 201; depending on the application, an adhesion promoter may be applied to facilitate spin coating of the photoresist prior to applying the first photoresist layer 201. Baking the substrate 200 at the temperature of 90-110 ℃ to remove the solvent in the photoresist; continuously spin-coating photoresist on the substrate 200 to form a second photoresist layer 202; baking the obtained substrate 200 at a temperature of 90-110 ℃, removing the solvent in the photoresist, and forming a double-layer photoresist on the substrate 200, as shown in fig. 2.
Simultaneously exposing the first photoresist layer 201 and the second photoresist layer 202 by using a mask 207, covering a pattern to be formed by the mask, and exposing the rest of the mask to light, so that the positive photoresist in the exposed first photoresist layer 201 and the exposed second photoresist layer 202 is dissolved in a positive developing solution, and the unexposed first photoresist layer 202 and the unexposed second photoresist layer 202 are not dissolved in the positive developing solution; there may be a soft baking step before the exposure treatment, and the exposure is followed by an exposure bake to allow the photochemical reaction to proceed more fully. Specifically, the first photoresist layer 201 is a positive photoresist, and includes a photosensitive acid generator and a resin; the resin can be one of Methyl Methacrylate (MMA), cycloolefin-maleic anhydride (COMA) and 2-ethyleneoxy ethyl methacrylate (VEMA); the photosensitive acid generator can be one of iodide (TBI-PFOS), sulfide (TPS-PFBS), triphenylsulfonium perfluorobutyl (TPS-Nf) and triphenylsulfonium triflurosulfonic acid (TPS-TF); further, the photoresist composition can comprise 7-8% of photosensitive acid generator, 30-40% of resin, 50-60% of solvent, 1% of photoresist additive and 1-2% of alkaline neutralizer; the solvent can be one of propylene glycol monomethyl ether ester (PGMEA), Ethyl Lactate (EL), Methyl Amyl Ketone (MAK) and Propylene Glycol Monomethyl Ether (PGME); the alkaline neutralizer is one of tetrabutylammonium hydroxide (TBAH), tetraethylammonium hydroxide (TEA), tetrapropylammonium hydroxide (TPA) and dodecylamine (TDDA); the second photoresist layer 202 is also a positive photoresist, and is different from the first photoresist layer in that the resin used in the second photoresist layer 202 is a phenolic resin, and other raw materials and proportions are the same as those of the first photoresist layer.
Exposing the substrate coated with the two layers of photoresist at an exposure dose of 20mj/cm2～25mj/cm2Exposing under the condition that the focal length is-0.05 um, forming a first exposure area 203 on the first photoresist layer 201, and forming a second exposure area 204 on the second photoresist layer 202; the width of the first exposure area 203 is equal to the width of the second exposure area 204, as shown in fig. 3.
Carrying out positive developing treatment on the image 3 by using a positive developing solution; specifically, a positive developing solution is sprayed onto the first and second photoresist layers 201 and 202, so that the exposure pattern is developed, i.e., the exposed photoresist layer is removed and the unexposed photoresist is left, thereby forming a first opening 205 of the first photoresist layer 201 and a second opening 206 of the second photoresist; wherein the width of the first opening 205 is equal to the width of the second opening 206, as shown in fig. 4. The positive developing solution may be a tetramethylammonium hydroxide (TMAH) solution, but it is understood by those skilled in the art that the positive developing solution is not limited thereto, and may be any positive developing solution suitable for the present invention, which can not dissolve the positive photoresist before exposure but can dissolve the positive photoresist after exposure, for example, some alkaline aqueous solutions, such as organic bases of tetraethylammonium hydroxide, but in order to avoid metal contamination, an alkaline developing solution with metal ions is not generally used.
Curing the second photoresist layer in fig. 4 with a curing agent, specifically, in this embodiment, 10% to 15% hexamethylene tetramine as the curing agent is used, and the curing is performed at a curing temperature of 150 ℃ to 170 ℃; the phenolic resin in the second photoresist layer 202 may react with hexamethylenetetramine to form a poorly soluble substance, forming a cured layer 208, as shown in fig. 5.
Performing negative development processing on fig. 5 by using a negative developing solution, specifically, spraying the negative developing solution on the surfaces of the first photoresist layer 201 and the second photoresist layer 202, dissolving the first photoresist layer 201 laterally by using the negative developing solution, and controlling the development time within 45s to 60s, so that the width of the first opening 205 is greater than that of the second opening 206, thereby obtaining an inverted T-shaped pattern with a narrow top and a wide bottom, as shown in fig. 6. The negative developer may be n-butyl acetate (NBA) or methyl isobutyl carbinol (MIBC), or any negative developer suitable for use in the present invention that dissolves the pre-exposure positive photoresist but not the post-exposure positive photoresist, e.g., ketone, ether, ester, hydrocarbon, or amide solvents.
After the development is completed, the developed pattern is usually washed, wherein the washing liquid after the development is an organic solvent, such as methyl isobutyl ketone (MIBK), 4-methyl-2-pentanol or isopropanol.
If the first opening 205 formed in the first photoresist layer is smaller than the width of the second opening 206 formed in the second photoresist layer, the negative developing process described in this embodiment may be used to perform the developing process, and the photoresist pattern shown in fig. 6 may be obtained.
In the embodiment, the negative developing process of the positive photoresist is adopted, the positive photoresist used for the negative developing process is used as the bottom photoresist of the double-layer photoresist, and the pattern shape can be accurately controlled to reach the inverted T-shaped pattern by utilizing the characteristic that the positive photoresist in the non-exposure area is dissolved in the negative developing solution, so that the secondary exposure of the required pattern is avoided, and the high resolution of the pattern is ensured.
Example 2
As shown in fig. 9, this embodiment discloses a bilayer photoresist stripping method based on embodiment 1.
On the basis of fig. 6, a metal film 209 is grown on the substrate 200 and its pattern by using a physical sputtering or evaporation method, as shown in fig. 7; the metal film 209 refers to a metal that is difficult to etch by a conventional wet or dry etching method, such as copper, gold, titanium, nickel, silver, platinum or chromium, but not limited to these metals; in order to prevent adhesion between the metal film 209 on the second photoresist and the metal film 209 on the substrate 200, the thickness of the metal film 209 is smaller than that of the first photoresist layer 201.
Removing the first photoresist layer 201 and the second photoresist layer 202 by using a photoresist stripping solution, removing the metal film 209 on the second photoresist layer 202 at the same time, and leaving the metal film 209 on the substrate 200 to form a metal film 209 pattern as a lead or an electrode of the semiconductor device, as shown in fig. 8; the photoresist stripping solution strips the two photoresist layers, wherein the photoresist stripping solution can be one or more of N-methyl pyrrolidone, gamma-butyrolactone or ethyl lactate.
In the embodiment, the negative developing process of the positive photoresist is adopted, and the shape of the pattern is accurately controlled to obtain the inverted T-shaped pattern with a narrow upper part and a wide lower part; and a metal pattern required by a lead or an electrode of the semiconductor device is manufactured by using the pattern; the method solves the problems of complex process for preparing metal patterns in the double-layer photoresist stripping process and the like.
The specific embodiments are only for explaining the invention, not for limiting the invention, and the skilled in the art can modify the embodiments as required after reading the description, but only by the protection of the patent law within the scope of the claims of the present invention.
Claims (12)
1. A method of patterning a photoresist, the method comprising:
sequentially forming a first photoresist layer and a second photoresist layer on a substrate;
exposing the first photoresist layer and the second photoresist layer simultaneously by using a mask;
carrying out positive development on the exposed first photoresist layer and the exposed second photoresist layer by using a positive developing solution to form a first opening and a second opening which are equal in width in the first photoresist layer and the second photoresist layer respectively;
and carrying out negative development on the first photoresist layer by adopting a negative developing solution, and increasing the width of the first opening to enable the width of the first opening to be larger than that of the second opening.
2. The method of claim 1, wherein the first photoresist layer and the second photoresist layer are both positive photoresists.
3. The method of claim 1, wherein the positive developing solution is tetramethylammonium hydroxide or tetraethylammonium hydroxide.
4. The method of claim 1, wherein the negative developing solution is n-butyl acetate or methyl isobutyl carbinol.
5. The method of claim 1, comprising, prior to negatively developing the first photoresist layer with a negative developer: and curing the second photoresist layer.
6. The method of claim 5, wherein the second photoresist layer comprises a photoacid generator and a phenolic resin, and the second photoresist layer is cured with hexamethylenetetramine.
7. The method of claim 6, wherein the hexamethylenetetramine is used in an amount of 10-15% and the curing temperature is 150-170 ℃.
8. The method of claim 1, wherein simultaneously exposing the first photoresist layer and the second photoresist layer using a reticle comprises: a focal length of-0.05 um to the first photoresist layer and the second photoresist layer is between 20mj/cm2～25mj/cm2The exposure dose of (a) is irradiated.
9. A double-layer photoresist stripping method is characterized by comprising the following steps:
forming a patterned first photoresist layer and a second photoresist layer on a substrate using the method of any one of claims 1-8;
forming a layer metal film on a substrate;
and removing the first photoresist layer and the second photoresist layer.
10. The bilayer photoresist stripping method of claim 9, wherein the thickness of the metal film is less than the thickness of the first photoresist layer.
11. The bilayer resist stripping process of claim 9, wherein the resist is subjected to a stripping solution using one or more of N-methylpyrrolidone, γ -butyrolactone or ethyl lactate.
12. The bilayer resist stripping method according to claim 9, wherein the metal film is made of copper, gold, titanium, nickel, silver, platinum or chromium.
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| CN113816335A (en) * | 2021-09-23 | 2021-12-21 | 华东光电集成器件研究所 | Metal stripping preparation method of silicon-based wafer double-layer photoresist |
| CN115541558A (en) * | 2022-12-02 | 2022-12-30 | 季华实验室 | SERS substrate manufacturing method and SERS substrate |
| CN115903401A (en) * | 2022-12-22 | 2023-04-04 | 上海铭锟半导体有限公司 | Super-resolution pattern implementation method and device based on etching and double photoetching |
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