WO2016114455A1 - 포토리소그래피 방법 - Google Patents

포토리소그래피 방법 Download PDF

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Publication number
WO2016114455A1
WO2016114455A1 PCT/KR2015/005768 KR2015005768W WO2016114455A1 WO 2016114455 A1 WO2016114455 A1 WO 2016114455A1 KR 2015005768 W KR2015005768 W KR 2015005768W WO 2016114455 A1 WO2016114455 A1 WO 2016114455A1
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WO
WIPO (PCT)
Prior art keywords
photoresist
light
ring
photoresist film
pattern
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/KR2015/005768
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English (en)
French (fr)
Inventor
유은아
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Korea Research Institute of Standards and Science
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Korea Research Institute of Standards and Science
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Publication date
Application filed by Korea Research Institute of Standards and Science filed Critical Korea Research Institute of Standards and Science
Priority to US14/895,180 priority Critical patent/US10108092B2/en
Publication of WO2016114455A1 publication Critical patent/WO2016114455A1/ko
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • 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
    • 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
    • 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
    • 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
    • G03F1/50—Mask blanks not covered by G03F1/20 - G03F1/34; Preparation thereof
    • 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
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
    • 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

Definitions

  • the present invention relates to a photolithography method, and more particularly, to a photolithography method capable of producing a ring pattern.
  • Lithography technology is capable of processing fine patterns on substrate materials.
  • nano / microscale lithography technology is an important core of the development and success of the semiconductor and display industries.
  • New technologies are needed to pattern high-level shapes such as fine ring patterns.
  • the present invention is to provide a photolithography method having an extremely simple structure, using a pre-built lithography process and equipment, to pattern an advanced shape such as a fine ring pattern, and to facilitate shape control of the ring. .
  • the photolithography method comprises the steps of: a) forming a photoresist film that satisfies the following relational formula 1; and b) a plate-type metal dot formed in contact with the light exit surface of the transparent substrate and the transparent substrate. and exposing the photoresist film and developing the exposed photoresist film by using a photomask including a metal dot to manufacture a ring-shaped photoresist pattern.
  • [?] D is the thickness of the photoresist film, n is the refractive index of the photoresist,? Is the wavelength of light irradiated upon exposure, and m is a natural number of 1 or more.
  • the optical mask satisfies the following relation 2
  • the interval between the photomask and the photoresist film may satisfy the following relation 3.
  • Equation 2 R is the radius of the flat metal dot.
  • Gap is the separation distance between the photomask and the photoresist film.
  • the metal of the flat metal dot is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb. Transition metals including Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt and Au; One or more selected from pre- and post-metals including Al, Ga, In, Tl, Sn, Pb and Bi; and metals including Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs and Baol; have.
  • the irradiated light may be ultraviolet (UV) light.
  • ultraviolet light of 90 to 110 mJ / cm 2 may be irradiated during the exposure.
  • the upper ring can be placed inside the lower ring.
  • the upper ring outer diameter of the shape may be smaller than the diameter of the metal dot.
  • the single-ring or multi-layer photoresist pattern is selected at least one of the dose and the development time of the light irradiated during the exposure. Can be controlled by a factor. '
  • the present invention provides a photoresist prepared using the photolithographic method described above. Contains a pattern.
  • the photolithography method according to the present invention enables the formation of highly detailed patterns such as fine ring patterns, but has the advantage of having an extremely simple structure of a flat transparent substrate and a flat metal dot. Thus, an expensive PSM mask is provided.
  • the advantage is that the photoresist can be patterned using low cost photomasks without using expensive equipment.
  • FIG. 1 is a scanning electron microscope photograph of a photoresist pattern manufactured according to an embodiment of the present invention.
  • FIG. 2 is a view showing a result of observing a photoresist pattern manufactured according to an embodiment of the present invention with an atomic force microscope (AFM), and FIG. 3 is another embodiment of the present invention.
  • FIG. 4 is a scanning electron micrograph of a photoresist pattern prepared according to another embodiment of the present invention.
  • the photoresist method according to the present invention comprises the steps of: a) forming a photoresist film satisfying the following relational formula on a substrate; and b) a flat metal dot formed in contact with the light exit surface of the transparent substrate and the transparent substrate. and exposing the photoresist film, developing the exposed photoresist film, and manufacturing a ring-shaped photoresist pattern using an optical mask including a plate-type metal dot.
  • D is the thickness of the photoresist film
  • ⁇ is the refractive index of the photoresist
  • ⁇ is the wavelength of light irradiated upon exposure
  • m is a natural number of 1 or more.
  • the thickness of the photoresist film that satisfies the condition of Equation 1 above is a condition in which a standing wave can be formed in the thickness direction of the photoresist film by resonance of light irradiated upon exposure.
  • a single layer to a plurality of rings can be laminated.
  • a layer-shaped photoresist pattern can be manufactured, and further, the thicknesses are similar to or the same.
  • a resist pattern can be produced.
  • the photoresist also applied to the substrate may be a photosensitive resin.
  • the photoresist may be a positive photosensitive resin which is soluble in chemicals by exposure to light, or may be exposed to chemicals by exposure to light. It may be a negative photosensitive resin that is soluble. That is, the photoresist also included in the substrate may be a positive photoresist or a negative photoresist.
  • the thickness of the photoresist coated on the substrate satisfies the above-mentioned relation 1, but m may be a natural number in which the thickness (D) of the photoresist is in the range of 50 nm to 500 nm.
  • the thickness of the photoresist is 50 nm. If it is too thin, the thickness of the remaining photoresist patterned in the form of a ring on the substrate becomes too thin, and the photoresist effectively acts as a mask during the subsequent process such as impurity injection into the substrate, etching of the substrate or deposition of substrate materials. It may not be possible.
  • the natural number m in relation (1 ) is the thickness of the photoresist (D) in terms of effective masking, preventing undesired yield reduction, and ensuring the quality of the cross-section, without compromising the quality of subsequent processes. ) Is better than the natural number so that it is in the range of 200 to 500 nm. Of course, it can be set properly.
  • the thickness (D) of the photoresist film is expressed in relation to the application and drying of the photoresist solution, soft baking, and hard baking. It means the thickness in the error category that occurs during the process of the normal photoresist forming process, and the thickness (average thickness) in the error category is 0.9% to 1.1% of D shown in relation 1, specifically 0.95. Can range from% to 1.05%.
  • the optical mask satisfies the following Equation 2, and the interval between the optical mask and the photoresist film may satisfy the following Equation 3.
  • Equation 2 R is the radius of the flat metal dot.
  • Gap is a separation distance between the photomask and the photoresist film.
  • Equations 2 and 3 are conditions under which a photoresist pattern having a shape parallel to that of a flat metal dot can be manufactured.
  • the radius of the flat metal dot is preferably 300 to 700 nm.
  • the height of the flat metal dot is sufficient to prevent the light from being exposed to exposure.
  • the height of the flat metal dot may be 50 nm to 150 nm.
  • the photoresist film has a thickness satisfying the relation 1,
  • Air concentration (gap, gap) is formed, so that light is concentrated in the center of the metal dot Regions may be formed and several photo-concentration regions may be formed spaced apart in the thickness direction of the photoresist.
  • the photoresist film satisfying the relation 1 may satisfy the relation 2
  • the planar metal is exposed to the photoresist film during exposure by making the surface direction in contact with the substrate deep in the photoresist film.
  • the first standing wave in which the concentration and extinction of light is repeated along the depth direction is formed in the shape of the flat metal dot in the area surrounded by the edge of the dot, and at the same time, the increase of the flat metal dot
  • the shape of the flat metal dot and the shape of the flat metal dot can be formed along the depth direction
  • the second normal wave can be formed to repeat the concentration and extinction of light along the depth direction, and the phase difference reaching 180 ° between the first and second normal wave That is, due to the phase difference reaching 180 °, the concentration of the light of the second standing wave occurs at the thickness of the photoresist where the light of the first standing wave occurs.
  • the above-mentioned first and second normal waves are formed in the photoresist film, and a plurality of rings are laminated in the thickness direction. It is possible to manufacture laminated laminated photoresist patterns.
  • the photoresist pattern obtained by exposure and phenomena may be a single layer shape or a laminar shape in which two or more rings are laminated.
  • the ring shape may have a shape in which both the shape of the inner void and the shape of the outer shape border the flat metal dot.
  • the second normal wave proceeds in parallel with the thickness direction and the thickness direction.
  • the width in the area where light is concentrated becomes narrower.
  • the first normal wave has a phase difference of 180 ° with the second normal wave, and the light increases as the thickness direction increases.
  • the width of the extinction area becomes wider.
  • the width of the light concentration area of the second normal wave affecting the inner diameter of the ring shape, and the width of the area where light disappears in the first normal wave, and may affect the outer diameter of the ring. have.
  • a laminated ring type photoresist pattern in which a plurality of rings are laminated can be manufactured. That is, in the multilayer ring photoresist pattern, each of the layers forming a multi-ring ring The ring has a concentric structure, and on the projection image in the direction of light irradiation, the upper ring can be located inside the lower ring.
  • the multi-layered rings form a concentric structure with each other, and the width of the ring located at the upper part (surface side to which light is irradiated) is relatively large.
  • Laminate (small) rings which are narrower than the width of the ring located at the lower (substrate side), are stacked.
  • a layered ring-shaped photoresist pattern can be produced.
  • At least the outer ring outer diameter of the multi-layer ring shape may be smaller than the diameter of the metal dot, wherein the upper outer ring diameter is a laminated ring in which two or more rings are laminated, except for the lowermost ring contacting the substrate. That is, it means a ring located on the uppermost ring.
  • the manufacturing method according to the embodiment of the present invention enables the production of a ring pattern having an outer diameter of 70% of the ring based on the diameter of the flat metal dot.
  • the photoresist pattern in the form of a lobed ring having an upper ring outer diameter including at least the uppermost part may be 70% to 96%, specifically 70 to 85%, based on the diameter of the metal dot.
  • the single-ring or multi-layer photoresist pattern is selected at least one of the dose and the development time of the light irradiated during the exposure. Can be controlled by a factor. '
  • a photoresist pattern having a single ring or a multi-layered ring shape may be manufactured by adjusting a dose of light irradiated during exposure.
  • the light concentration areas of the first normal wave may be combined with each other.
  • the boundary between the light concentration areas may become unclear and a monolayer ring pattern may be manufactured.
  • the amount of light used as a boundary between the multilayer ring pattern and the single layer ring pattern may vary depending on the type of photoresist and development conditions. However, in order to stably manufacture a multi-layered loop pattern, 1 10 mJ / cm 2 or less It is better to irradiate 105mJ / cm 2 light stably.
  • the dose of light irradiated during exposure should be higher than that of the photoresist film (that is, the exposure can be performed to the bottom surface of the photoresist, which is a surface in contact with the substrate).
  • the dose of light emitted during exposure can be at least 90 mJ / cm 2, preferably at least 95%.
  • the photoresist pattern in the form of a single layer or a multi-layer ring
  • amount of light to be irradiated is from 90 to l lOmJ / cm 2, better is the number of days of 95 to 105mJ / cm 2. Substantially developing time, regardless of the past, a single-layer ring of the photoresist by the light amount is irradiated When manufacturing a pattern, the amount of light irradiated during exposure is greater than lOmJ / cm 2 , more stably.
  • a light amount of light exceeding 1 15 mJ / cm 2 can be irradiated.
  • the development time can be adjusted to selectively manufacture single to multi-layer loop patterns.
  • the development time determines the type of photoresist and the type of developer used for development.
  • the phenomenon can be performed for 10 to 100 seconds.
  • the phenomenon can be performed for more than a second.
  • the substrate before the exposure step is performed, applying a photoresist to the substrate to form a photoresist film to satisfy the relation 1; at this time, the substrate may be performed In addition to the role of the support, it may be a substrate on which other components are formed depending on the purpose of manufacturing the electronic device, the optical device, or the sensor.
  • the non-limiting example of the other components may include a partially impurity doped region and a recess structure. Also, but not limited to, via hole structures.
  • the substrate may be in the form of a wafer or a film, and may be a semiconductor, a ceramic, a metal, a polymer, or a laminate of two or more layers selected from each other.
  • the silicon substrate may be a non-limiting example of a semiconductor substrate.
  • Group IV semiconductor gallium arsenide containing (Si), germanium (Ge) or silicon germanium (SiGe), group 3-5 semiconductor cadmium sulfide (CdS) containing indium phosphorus (InP) or gallium phosphorus (GaP) or Group 4-6 semiconductors containing lead 2-6 semiconductor sulfide sulfide (PbS) containing zinc telluride (ZnTe), or two or more materials selected from them, each layered and stacked laminates.
  • GaAs Group IV semiconductor gallium arsenide
  • Si germanium
  • SiGe silicon germanium
  • InP indium phosphorus
  • GaP gallium phosphorus
  • PbS semiconductor sulf
  • the photoresist (photosensitive resin) may be positive type or
  • the exposure step may be performed by placing a photomask between the light source and the substrate on which the photoresist film is formed so that the transparent substrate side on which the flat metal dot is located is the light exit surface.
  • the photomask may include a transparent substrate and a flat metal dot.
  • the photomask may consist of a transparent substrate and a flat metal dot, or may be made of a transparent substrate, a flat metal dot and a protrusion described later.
  • the transparent substrate has light incident on one of the two opposite surfaces of the transparent substrate and the light exiting on the other surface.
  • the transparent substrate may be a plane having at least a light emitting surface.
  • it may be a transparent plate shape in which both the entrance and exit planes of light are flat.
  • the transparent substrate may be a material used as a light-transmitting substrate in a normal photolithography photomask.
  • the transparent substrate may be quartz, but the present invention is not limited thereto.
  • the transparent substrate transmits light and is sufficient if the mask has a typical thickness of the substrate on which the light is transmitted in a physical photolithography mask.
  • the thickness of the transparent substrate may be several ⁇ to several tens of mm. , The present invention is not limited to this.
  • the flat metal dot can be positioned in contact with the transparent substrate on the light exit surface of the transparent substrate.
  • the outline of the flat metal dot (border shape) and the main beam are performed. It is possible to manufacture the ring pattern of the shape.
  • At least one flat metal dot is circular; elliptic; and polygonal;
  • the polygon may have a triangular to octagonal, in detail, triangular, square (rectangular or square), pentagonal, hexagonal, hexagonal or octagonal. Polygons can be patterned.
  • the optical mask may be a flat metal dot unit, and two or more units are arranged on the light exit surface of the transparent substrate.
  • the flat metal dot array may include a regular array or an irregular array.
  • the array of flat metal dots Of course, it can be properly adjusted considering the designed structure to be patterned.
  • the metals of the flat metal dots are Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Transition metals including La, Hf, Ta, W, Re, Os, Ir, Pt and Au;
  • One or more may be selected from pre and post metals including At, Ga, In, TI, Sn, Pb and Bi and metals including Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs and Ba
  • the metal of the flat metal dot is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd
  • One or more may be selected from transition metals including La, Hf, Ta, W, Re, Os, Ir, Pt and Au. More specifically, the metal of the flat metal dot may be Cr.
  • the photomask is a region that does not affect the patterning of the photoresist film, and in one example, in the edge region of the transparent substrate,
  • the projections may further include protrusions that allow the nanogap (air gap) to be formed at a stable and predetermined value.
  • the height of the protrusion may be the sum of the height of the planar metal dot formed on the photomask and the gap according to Equation 3.
  • exposure can be performed by irradiating light with a dose of at least 90 mJ / cm 2 or more as described above.
  • the irradiated light may be ultraviolet (UV) light, and may be ultraviolet light in a wavelength band of lOnm to 500 nm. Specifically, the irradiated light has a center wavelength of 300 mN.
  • UV ultraviolet
  • the irradiated light has a center wavelength of 300 mN.
  • the manufacturing method according to one embodiment of the present invention is conventionally used in conventional photolithography processes. Exposure can be carried out using ultraviolet rays comprising wavelengths of I-line, H-line and / or G-line used. The exposure step is also performed using optical means commonly used in photolithography processes. This is because the photolithography method according to the present invention can utilize photoresist, exposure apparatus and the like which are commonly used in conventional photolithography processes as well as photomasks.
  • the developing step includes a developing solution ordinarily used in a photolithography process.
  • the developing step is performed by using a developer containing a solvent that melts and removes a photosensitive resin portion whose chemical properties have been changed by exposure, and thus, a photosensitive resin portion having a changed chemical characteristic. Can be achieved by removing By controlling the development time, a photoresist pattern of a single layer or a multi-layer ring phenomenon can be manufactured.
  • the step of removing the photoresist may be further performed.
  • the removal of the remaining photoresist may be performed using materials and methods commonly used for the removal of the photoresist developed in the photolithography process.
  • 1 is a scanning electron micrograph of the photoresist pattern produced by the manufacturing method of the present invention.
  • FIG. 2 is a diagram showing the results of observing the manufactured ring-type photoresist pattern with an atomic force microscope (AFM).
  • AFM atomic force microscope
  • the photoresist is patterned in the form of a hollow ring using a mask in which a flat metal dot is formed on a transparent substrate in a flat plate shape, not an expensive PSM. It can be seen that a single-walled micropattern pattern having an outer diameter of 1.86 ⁇ and a ring width of 667 nm is manufactured.
  • FIG. 3 is manufactured in the same manner as the photoresist pattern observed in FIG. 1, but performs the development for 62 seconds to observe the photoresist pattern produced.
  • FIG. 4 is a scanning electron microscope photograph
  • FIG. 4 is a scanning electron microscope photograph of the photoresist pattern manufactured by performing the same method as the photoresist pattern observed in FIG. 1 and performing for 17 seconds.
  • the manufacturing method of the present invention has a concentric structure, and as the upper portion thereof is located, it can be seen that a multi-layered ring pattern is manufactured.
  • the photoresist pattern was manufactured in the same manner as the photoresist pattern observed in FIG. 1, but the exposure was performed so that the amount of light to be irradiated was l UmJ / cm 2. I confirmed it.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

본 발명에 따른 포토리소그래피 방법은 a)기판상 D=m*(λ/2n) (D=포토레지스트 막의 두께， n=포토레지스트의 굴절률， λ=노광시 조사되는 광의 파장， m= 1이상의 자연수)을 만족하는 포토레지스트 막을 형성하는 단계;및 b)투명 기재 및 투명 기재의 광의 출사면에 접하여 형성된 평판형 금속 닷 (plate-type metal dot)을 포함하는 광 마스크를 이용하여, 포토레지스트 막을 노광하고，노광된 포토레지스트 막을 현상하여，고리 형상의 포토레지스트 패턴을 제조하는 단계;를 포함한다.

Description

명세서
발명의명칭:포토리소그래피방법
기술분야
[1] 본발명은포토리소그래피방법에관한것으로,상세하게,고리패턴의제조가 가능한포토리소그래피방법에관한것이다.
배경기술
[2] 리소그래피 (lithography)기술은대상기재에미세패턴을가공할수있는
방법으로，나노 /마이크로스케일의리소그래피기술은반도체및디스플레이 산업의발전과성패를좌우하는중요한핵심기술이다.
[3] 미세패터닝에있어,근본적으로부딪히게되는제한요인은리소그래피에
사용되는빛의파장으로， 0.8/zm이상의선폭을갖는회로의경우에는수은 UV 램프를사용하였으나，그이하의선폭을패터닝하기위해서는새로운광원이 필요하게되었고， KrF (Kripton Fluoride)액시머레이저 (파장 =248nm)를이용하여 O. MII공정이가능해졌으며， 90nm이하의공정이필요해짐에따라 ArF (Argon Fluoride)액시머레이저 (파장 =193nm)가사용되고있다.
[4] ArF액시머레이저보다더짧은파장을이용하기위해서는불소엑시머
레이저 (파장 =157nm)를사용하여야하나,렌즈시스템의개구수 (numerical aperture)가낮아지는등의다양한문제가발생하고있으며，극자외선올이용하는 경우매우고가의포토마스크가필요하여상업적인한계가있으며,전자빔을 이용하는경우작업속도가매우느리고장비가격또한높아실용화에걸림돌이 되고있다.
[5] 나아가，대한민국공개특허제 2010-0076680호에제시된바와같이，제조하고자 ' 하는미세패턴이링 (원형고리)형태와같이고도해지는경우,복잡한표면 요철이나미세구조가형성된고가의 PSM(phase shift Mask)이사용되고있다. 그러나,이러한방법은고가의마스크설계와제작및리소그래피를위한별도의 광학시스템의개발이불가피하여막대한비용및연구개발이선행되어야하는 단점이있다.
[6] 상술한바와같이,저비용으로，기구축된리소그래피공정및장비를
이용하여 ,미세고리패턴과같은고도의형상을패터닝할수있는새로운 기술이요구되고있다.
발명의상세한설명
기술적과제
[7] 본발명은극히간단한구조를가지며,기구축된리소그래피공정및장비를 이용하여,미세고리패턴과같은고도의형상을패터닝할수있으며，고리의 형상제어가용이한포토리소그래피방법을제공하는것이다.
과제해결수단 [8] 본발명에따른포토리소그래피방법은 a)기판상하기관계식 1을만족하는 포토레지스트막을형성하는단계;및 b)투명기재및투명기재의광의 출사면에접하여형성된평판형금속닷 (plate-type metal dot)을포함하는광 마스크를이용하여，포토레지스트막을노광하고，노광된포토레지스트막을 현상하여,고리형상의포토레지스트패턴을제조하는단계;를포함한다.
[9] (관계식 1)
[10] D=m*(X/2n)
[Π] D는포토레지스트막의두께이며， n은포토레지스트의굴절률이며 , λ는노광시 조사되는광의파장이며, m은 1이상의자연수이다.
[12] 본발명의일실시예에따른포토리소그래피방법에있어，상기광마스크는 하기관계식 2를만족하며,상기광마스크와상기포토레지스트막간의간격은 하기관계식 3을만족할수있다.
[13] (관계식 2)
[14] 150nm < R < 1.5μπι
[15] 관계식 2에서， R은평판형금속닷의반지름이다.
[16] (관계식 3)
[17] 50nm < Gap < 200 nm
[18] 관계식 3에서， Gap는광마스크와포토레지스트막간의이격거리이다.
[19] 본발명의일실시예에따른포토리소그래피방법에있어，상기평판형금속 닷의금속은 Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt및 Au를포함하는전이금속; Al, Ga, In, Tl, Sn, Pb및 Bi를포함하는전이후금속;및 Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs및 Ba올 포함하는금속;에서하나이상선택될수있다.
[20] 본발명의일실시예에따른포토리소그래피방법에있어，상기노광시
조사되는광은자외선 (UV)일수있다.
[21] 본발명의일실시예에따른포토리소그래피방법에있어，상기노광시 90내지 110 mJ/cm2광량의자외선이조사될수있다.
[22] 본발명의일실시예에따른포토리소그래피방법에있어,상기포토레시스트 패턴은단층고리형상또는둘이상의고리가적층된다층고리형상이며,상기 다충고리형상의각고리는동심구조를가지며，광조사방향으로의
투사 (projection)이미지상,상부고리가하부고리내부에위치할수있다.
[23] 본발명의일실시예에따른포토리소그래피방법에있어，상기다층고리
형상의상부고리외경은상기금속닷의직경보다작을수있다.
[24] 본발명의일실시예에따른포토리소그래피방법에있어，상기단층고리형상 또는다층고리형상의포토레시스트패턴은상기노광시조사되는광의 광량 (dose)및현상시간중적어도하나이상선택되는인자에의해조절될수 있다. '
[25] 본발명은상술한포토리소그래피방법을이용하여제조된포토레지스트 패턴을포함한다.
발명의효과
[26] 본발명에따른포토리소그래피방법은미세고리패턴과같은고도한형상의 패턴화가가능하면서도,평판형투명기재와평판형금속닷이라는극히간단한 구조를갖는장점이있다.이에따라，고가의 PSM마스크나고가의장비를 사용하지않고，저가의광마스크를이용하여포토레지스트의고리패턴화가 가능한장점이있다.
[27] 또한，본발명에따른포토리소그래피방법은평판형금속닷의크기보다작은 크기를갖는고리패턴의제조가가능한장점이있으며，동일한광마스크를 이용하여，조사되는광의광량이나현'상시간을조절함으로써，다양한형상의 고리패턴을제조할수있는장점이있다.
[28] 또한,마스크를제외하고종래통상적으로사용되는노광장치 ,노광방법， 포토레지스트,현상액및현상방법을사용할수있음에따라，종래기구축된 포토리소그래피공정의변경없이활용가능한장점이있다.
도면의간단한설명
[29] 도 1은본발명의일실시예에따라제조된포토레지스트패턴을관찰한일 주사전자현미경사진이며，
[30] 도 2는본발명의일실시예에따라제조된포토레지스트패턴을원자간력 현미경 (AFM; Atomic Force Microscope)으로관찰한결과를도시한도면이며, [31] 도 3은본발명의다른일실시예에따라제조된포토레지스트패턴을관찰한 주사전자현미경사진이며，
[32] 도 4는본발명의또다른실시예에따라제조된포토레지스트패턴을관찰한 주사전자현미경사진이다ᅳ
[33]
발명의실시를위한형태
[34] 이하첨부한도면들을참조하여본발명의포토리소그래피방법을상세히 설명한다.다음에소개되는도면들은당업자에게본발명의사상이충분히 전달될수있도록하기위해예로서제공되는것이다.따라서，본발명은이하 제시되는도면들에한정되지않고다른형태로구체화될수도있으며，이하 제시되는도면들은본발명의사상을명확히하기위해과장되어도시될수 있다.이때，사용되는기술용어및과학용어에있어서다른정의가없다면，이 발명이속하는기술분야에서통상의지식을가진자가통상적으로이해하고 있는의미를가지며，하기의설명및첨부도면에서본발명의요지를
불필요하게흐릴수있는공지기능및구성에대한설명은생략한다.
[35] 본출원인은포토리소그래피를이용하여미세한고리형상의패턴을형성하기 위한연구를수행한결과,놀랍게도인위적인표면요철이형성되지않은평판 형태의투명기재의광출사면에평판형금속닷이형성된극히간단한구조의 마스크로도，단층내지다층의고리패턴의형성이가능함을발견하였으며， 나아가,평판형금속닷의직경보다도작은외경을갖는고리패턴의제조가 가능함을발견하고，이를심화하여본발명을완성하기에이르렀다.
[36] 상세하게，본발명에따른포토레지스트방법은 a)기판상하기관계식 1올 만족하는포토레지스트막을형성하는단계;및 b)투명기재및투명기재의 광의출사면에접하여형성된평판형금속닷 (plate-type metal dot)을포함하는광 마스크를이용하여，포토레지스트막을노광하고,노광된포토레지스트막을 현상하여，고리형상의포토레지스트패턴을제조하는단계;를포함한다.
[37] (관계식 1 )
[38] D=m*( /2n)
[39] D는포토레지스트막의두께이며 , η은포토레지스트의굴절률이며， λ는노광시 조사되는광의파장이며, m은 1이상의자연수이다.
[40] 상기관계식 1의조건을만족하는포토레지스트막의두께는,노광시조사되는 광의공진 (resonance)에의해，포토레지스트막의두께방향으로정상파 (standing wave)가형성될수있는조건이다.
[41] 상술한관계식 1을만족함으로써，단층내지다수개의고리가적층된다층고리 형상의포토레지스트패턴이제조될수있으며，나아가，두께가서로유사내지 동일한다수개의고리들이적층된적층고리형상의포토레지스트패턴이 제조될수있다.
[42] 기재에도포되는포토레지스트는감광성수지일수있다.감광성수지는
통상의리소그래피공정에사용되는광에의해약품에대한내성이변화되는 고분자물질이면무방하다.포토레지스트는광에노출됨으로써약품에대하여 가용성이되는포지티브형감광성수지이거나,광에노출됨으로써약품에 대해서블용성이되는네거티브형감광성수지일수있다.즉,기재에도포되는 포토레지스트는포지티브포토레지스트또는네거티브포 £레지스트일수 있다.
[43] 기재에도포된포토레지스트의두께는상술한관계식 1을만족하되，자연수인 m은포토레지스트의두께 (D)가 50nm내지 500nm범위에속하는자연수일수 있다.이는,포토레지스트의두께가 50nm미만으로너무얇은경우기재에고리 형태로패턴화되어잔류하는포토레지스트의두께가너무얇아져，기재에의 불순물주입，기재의식각또는기재상물질증착과같은후속공정시， 포토레지스트가마스크역할을효과적으로수행하지못할수있기때문이다. 또한，기재에도포된포토레지스트의두께가 500nm를초과하여너무두꺼운 경우,포토리소그래피이후의후속공정시마스크역할은효과적으로수행할수 있으나，포토레지스트에의한너무큰표면단차가기재에형성되어，원하는 영역에균일하고균질하게후속공정이수행되지못할위험이있을뿐만아니라, 노광공정시불량이발생할위험이높아지며，이에따라현상시포토레지스트의 현상단면의질이떨어질위험이있다. [44] 후속공정의질을저하시키지않으면서효과적으로마스크역할을수행하고， 원치않는수율감소를방지할수있으며，현상단면의질을담보하는측면에서， 관계식 1의자연수 m은포토레지스트의두께 (D)가 200내지 500nm범위에 속하도록하는자연수인것이보다좋다.상술한바와같이，조사되는광의 파장 (중심파장)과포토레지스트의굴절률을고려하여，상술한바람직한 포토레지스트의두께를갖도록자연수 m이적절히설정될수있음은물론이다. 통상의포토리소그래피공정에사용되는자외선광의파장과통상의
포토레지스트굴절률을고려할때，구체적이고비한정적인일예로, m = 2내지 7일수있다.이때，관계식 1에서，포토레지스트막의두께 (D)는감광성수지 용액의도포및건조，소프트베이킹，하드베이킹등과같은통상의포토레지스트 형성공정의공정상발생하는오차범주내에서의두께를의미하는것이며, 이러한오차범주내의두께 (평균두께)는관계식 1로제시된 D의 0.9%내지 1.1%,구체적으로는 0.95%~1.05%의범주에속할수있다.
[45] 본발명의일실시예에따른포토리소그래피방법에있어 ,상기광마스크는 하기관계식 2를만족하며，상기광마스크와상기포토레지스트막간의간격은 하기관계식 3을만족할수있다.
[46] (관계식 2)
[47] I50nm < R < 1.5μπι
[48] 관계식 2에서， R은평판형금속닷의반지름이다.
[49] (관계식 3)
[50] 50nm < Gap < 200 nm
[51] 관계식 3에서， Gap는광마스크와포토레지스트막간의이격거리이다.
[52] 관계식 2및관계식 3은,평판형금속닷과대웅되는형상을갖되,속이빈고리 형상을갖는포토레지스트패턴이제조될수있는조건이다.
[53] 구체적으로，관계식 2에서제시한바와같이,평판형금속닷의최대반지름이
1.5μηι를초과하거나，평판형금속닷의최소반지름이 150nm미만인경우，노광 및현상을통해목적하는고리형상의포토레지스트패턴이제조되지않을 위험이있다.
[54] 평판형금속닷의형상에잘대응되는형상으로고리형상의패턴을제조하기 위해，평판형금속닷의반지름은 300내지 700nm인것이보다좋다.
[55] 이때，평판형금속닷의높이는노광시조사되는광의투과가방지될수있는 두께이면족하다.구체적이며비한정적인일예로，평판형금속닷의높이는 50nm내지 150nm일수있다.
[56] 상술한바와같이，관계식 2를만족함과동시에，광마스크와포토레지스트간 관계식 3을만족하는극히미세한갭이형성되는것이좋다.
[57] 포토레지스트막이관계식 1을만족하는두께를가지면서，관계식 2를
만족하는평판형금속닷과함께，관계식 3을만족하는 200nm이하의
공기층 (이격간격，갭)이형성됨으로써,금속닷의중심에광이집중되는광집중 영역이형성될수있으며，포토레지스트의두께방향으로서로이격된다수개의 광집증영역이형성될수있다.
[58] 이에따라，관계식 1을만족하는포토레지스트막에，관계식 2를만족하는
평판형금속닷이형성된광마스크를이용하여，관계식 3을만족하는나노 에어갭이형성되도록하여，노광을수행하는경우，단층고리형태의패턴뿐만 아니라，다수개의고리들이서로적층된적층고리형태의패턴또한제조될수 있다.
[59] 구체적으로，관계식 1，관계식 2및관계식 3을만족하는경우,포토레지스트 막에서광이조사되는면에서기판에접한면방향을깊이방향으로하여, 노광시포토레지스트막에는，평판형금속닷의테두리에대웅되는영역에 평판형금속닷의형상과대웅되는형상으로，깊이방향을따라광의집중과 소멸이반복되는제 1정상파 (standing wave)가형성되며,이와동시에，평판형 금속닷의증심에대응되는영역에평판형금속닷의형상과대웅되는형상으로， 깊이방향을따라광의집중과소멸이반복되는제 2정상파가형성될수있으며, 제 1정상파와제 2정상파간 180°에이르는위상차가형성될수있다.즉, 180°에 이르는위상차에의해，제 1정상파의광의소멸이발생하는포토레지스트의 두께에서는제 2정상파의광의집중이발생하게된다.
[60] 본발명의일실시예에따른제조방법은관계식 1,관계식 2및관계식 3에의해， 상술한제 1정상파와계 2정상파가포토레지스트막에형성되어,다수개의 고리들이두께방향으로적층된적층고리형포토레지스트패턴의제조가 가능하다.
[61] 즉，본발명의일실시예에따른제조방법에서 ,노광및현상에의해수득되는 포토레시스트패턴은단층고리형상또는둘이상의고리가적층된다층고리 형상일수있다.이때，상술한바와같이，고리형상은내측형상인빈공극의 형상과외측형상인테두리의형상이모두평판형금속닷과대웅하는형상을 가질수있다.
[62] 또한，본발명의일실시예에따른제조방법에있어，관계식 2의광마스크를 이용하여관계식 3을만족하도록노광을수행하는경우,제 2정상파는두께 방향과평행하게진행하며，두께방향이증가할수록광이집중되는영역에서의 폭 (깊이방향에수직인방향의폭)이좁아지게된다.이와동시에,제 1정상파는 제 2정상파와 180°의위상차를가지며，두께방향이증가할수록광이소멸되는 영역의폭이넓어지게된다.제 2정상파의광집중영역의폭이고리형상의 내경에영향을미치며，제 1정상파에서광이소멸되는영역의폭이고리의 외경에영향을미칠수있다.
[63] 이에따라，상술한제 1정상파와제 2정상파에의해,동심구조를갖되 ,
상부 (광이조사되는표면측)로갈수록그외경이작아지고내경이커지는 다수개의고리가적층된적층고리형태의포토레지스트패턴이제조될수있다. 즉，상기다층고리형상의포토레지스트패턴에서，다층고리를이루는각 고리는동심구조를가지며，광조사방향으로의투사 (projection)이미지상，상부 고리가하부고리내부에위치할수있다.
[64] 즉，일고리의외경와내경의차를고리의폭이라할때，다층고리형상은서로 동심구조를이루며적층되되,상대적으로상부 (광이조사되는표면측)에 위치하는고리의폭이상대적으로하부 (기판측)에위치하는고리의폭보다 좁은 (작은)고리들이적층된다층고리형상의포토레지스트패턴이제조될수 있다.
[65] 보다놀라운것은，관계식 2를만족하는극히미세한평판형금속닷이형성된 마스크를이용하여,마스크와포토레지스트간관계식 3을만족하는나노 ¾이 형성되는조건에서노광을수행하는경우，평판형금속닷보다도그외경이작은 극미세의고리형태의패턴이제조될수있는점이다.
[66] 구체적으로，상기다층고리형상의적어도상부고리외경은상기금속닷의 직경보다작을수있다.이때，상부고리외경은둘이상의고리가적층된적층형 고리에서，기판과접하는최하부고리를제외한고리,즉,최하부고리상부에 위치하는고리를의미한다.
[67] 보다구체적으로,본발명의일실시예에따른제조방법은평판형금속닷의 직경을기준으로, 70%에이르는고리의외경을갖는고리패턴의제조가 가능하다.상세하게，적층형고리형상에서，적어도최상부를포함한상부고리 외경이상기금속닷의직경올기준으로 70%내지 96%,구체적으로 70내지 85%에이르는적충형고리형태의포토레지스트패턴이제조될수있다.
[68] 본발명의일실시예에따른포토리소그래피방법에있어，상기단층고리형상 또는다층고리형상의포토레시스트패턴은상기노광시조사되는광의 광량 (dose)및현상시간중적어도하나이상선택되는인자에의해조절될수 있다. '
[69] 상세하게，본발명의일실시예에따른제조방법에있어,상기노광시조사되는 광의광량 (dose)을조절하여，단층고리내지다층고리형태의포토레지스트 패턴이제조될수있다.
[70] 조사되는광의광량을일정광량이상으로증가시키는경우,제 1정상파의광 집증영역들이서로결합될수있는데，이러한경우광집중영역간의경계가 불명확해지며단층의고리패턴이제조될수있다.
[71] 즉,조사되는광의광량을제 1정상파의광집중영역들이두께방향으로서로 결합하는정도의높은광량을조사하는경우，단층의고리패턴을제조할수 있으며，반면,포토레지스트막의두께방향으로，광집증영역과광소멸영역이 교번형성되도록낮은광량으로광을조사함으로써，다층의고리패턴이제조될 수있다.
[72] 다층의고리패턴과단층의고리패턴이형성되는경계가되는광량 (dose)은 포토레지스트의종류,현상조건등올고려하여어느정도가변될수있다. 그러나，안정적으로다층고리패턴을제조하기위해서는, 1 10mJ/cm2이하，보다 안정적으로는 105mJ/cm2의광량이조사되는것이좋다.
[73] 이때,노광시조사되는광의광량 (dose)은,포토레지스트막을충분히노광할수 있을정도 (즉,기판과접하는면인포토레지스트최하부면까지노광이수행될 수있을정도)의광량이상이어야함은물론이다.이러한측면에서，노광시 조사되는광의광량 (dose)은최소 90mJ/cm2이상,좋게는 95%이상일수있다.
[74] 상술한바와같이，단층내지다층고리형태의포토레지스트패턴을
제조하고자하는경우，조사되는광의광량은 90내지 l lOmJ/cm2,좋게는 95내지 105mJ/cm2일수있다.조사되는광의광량에의해실질적으로현상시간과거의 무관하게,단층고리형태의포토레지스트패턴을제조하고자하는경우，노광시 조사되는광의광량은 l lOmJ/cm2을초과하는광량，보다안정적으로는
1 15mJ/cm2을초과하는광량의광이조사될수있다.
[75] 또한，다층고리가형성될수있는광량 (일정광량)으로노광을수행한
경우에도,현상시간을조절하여,단층내지다층고리패턴을선택적으로 제조할수있다.
[76] 이는,다층고리가형성되는일광량으로노광을수행한경우라도,상부고리에 해당하는포토레지스트영역과하부고리에해당하는포토레지스트영역간 결합된부분이현상에의해제거될수있을정도로상대적으로장시간동안 현상을수행하여단층고리패턴을제조할수있음을의미하며,또힌,상부 고리에해당하는포토레지스트영역과하부고리에해당하는포토레지스트 영역간결합된부분이현상에의해제거되지않을정도로상대적으로단시간 동안현상을수행하여다층고리패턴을제조할수있음을의미한다.
[77] 현상시간은포토레지스트의종류，현상에사용되는현상액의종류등을
고려하여，적절히변경가능하나，구체적인일예로，다층의고리형태를 제조하고자하는경우 10초내지 100초동안현상이수행될수있으며，단층의 고리형태를제조하고자하는경우 100초이상，안정적으로는 150초이상동안 현상이수행될수있다.
[78] 본발명의일실시예에따른제조방법에있어，노광단계가수행되기전，기판에 포토레지스트를도포하여관계식 1을만족하도록포토레지스트막을형성하는 단계;가수행될수있다.이때,기판은지지체의역할뿐만아니라，전자소자, 광학소자또는센서등의제조하고자하는물의용도에따라다른구성요소가기 형성된기재일수있다.다른구성요소의비한정적인일예로，부분적불순물 도핑영역,리세스구조，비아홀구조둥을들수있으나，이에한정되는것은 아니다.
[79] 기판은웨이퍼또는필름 (film)형상일수있으며 ,반도체,세라믹 ,금속，고분자 또는이들에서선택된둘이상의물질이각층을이루며적층된적층체일수 있다.반도체기재의비한정적인일예로,실리콘 (Si),게르마늄 (Ge)또는 실리콘게르마늄 (SiGe)을포함하는 4족반도체갈륨비소 (GaAs),인듐인 (InP)또는 갈륨인 (GaP)을포함하는 3-5족반도체황화카드뮴 (CdS)또는 텔루르화아연 (ZnTe)을포함하는 2-6족반도체황화납 (PbS)을포함하는 4-6족 반도체또는이들에서선택된둘이상의물질이각층을이루며적층된적층체를 들수있다.
[80] 상술한바와같이 ,포토레지스트 (감광성수지 )는포지티브형또는
네가티브형일수있으며,기판상스핀코팅등을포함한통상의공정을이용하여 감광성수지의도포가이루어진후，도포된수지층의건조 (소프트베이킹)가 수행될수있으며，선택적으로하드베이킹이수행될수있다.이때，도포된 포토레지스트막이에어 ¾을통해광마스크과직접대면하도록，
포토레지스트막상에이종의막이형성되지않는것이좋다.
[81] 노광단계는평판형금속닷이위치하는투명기재측이광의출사면이되도록 광마스크를광원과포토레지스트막이형성된기판사이에위치시킨후，광을 조사하여수행될수있다ᅳ
[82] 상술한바와같이，광마스크는투명기재및평판형금속닷을포함할수있다. 상술한본발명의장점에의해，광마스크는투명기재및평판형금속닷으로 이루어지거나，또는투명기재 ,평판형금속닷및후술하는돌출부로이루어질 수있다.
[83] 투명기재는，투명기채의두대향면중일면에광이입사되고，다른일면에 광이출사된다.본발명의일실시예에있어，투명기재는적어도광의출사면이 편평한평면일수있으며，나아가，광의입사면과출사면이모두편평한평면인 투명판형상일수있다.
[84] 투명기재는통상의포토리소그래피용포토마스크에서광이투광되는기재로 사용되는물질이면족하다.일예로,투명기재는석영 (quartz)일수있으나,본 발명이이에한정되는것은아니다.
[85] 투명기재는광을투과하며마스크에물리적통상의포토리소그래피용포토 마스크에서광이투광되는기재가갖는통상적인두께를가지면족하다.일 예로，투명기재의두께는수 μηι내지수십 mm일수있으나，본발명이이에 한정되는것은아니다.
[86] 평판형금속닷은투명기재의광의출사면에투명기재에접하여위치할수 있다.광마스크를이용한포토레지스트의노광및현상올수행하는경우， 평판형금속닷의윤곽 (테두리의모양)과대웅되는형상의고리패턴을제조할 수있다.
[87] 구체적으로，평판형금속닷은원형;타원형；및다각형;에서하나이상
선택되는형상을가질수있다.이때,다각형은삼각내지팔각，상세하게,삼각， 사각 (직사각또는정사각)，오각，육각,칠각또는팔각을포함한다.이에따라， 원형고리，타원형고리또는삼각내지팔각의다각고리를패턴화할수있다.
[88] 또한，광마스크는평판형금속닷을일단위체로,투명기재의광출사면에둘 이상의단위체가배열된것일수있다.이러한평판형금속닷의배열은규칙적 배열또는불규칙적배열을포함할수있으며，평판형금속닷의배열은 패턴화하고자하는설계된구조를고려하여적절히조절될수있음은물론이다.
[89] 평판형금속닷의금속은 Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt및 Au를포함하는전이금속; At, Ga, In, TI, Sn, Pb및 Bi를포함하는전이후금속및 Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs및 Ba을포함하는금속;에서하나이상선택될수있다.구체적으로，평판형 금속닷의금속은 Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt및 Au를포함하는전이금속에서하나 또는둘이상선택될수있다.보다구체적으로，평판형금속닷의금속은 Cr일수 있다.
[90] 이때，광마스크는포토레지스트막의패턴화에영향을미치지않는영역, 실질적인일예로，투명기재의가장자리영역에，관계식 3에따르는
나노갭 (에어갭)이안정적이며기규정된값으로형성되도록하는돌출부를더 포함할수있다.
[91] 돌출부는광마스크와포토레지스트막간의이격거리 (Gap=광마스크와
포토레지스트막간의거리 =평판형금속닷과포토레지스트막간의거리)를 조절하는역할을수행함에따라，돌출부의높이는광마스크에형성된평판형 금속닷의높이와관계식 3에따른 Gap을합한값일수있다.상술한돌출부에 의해,광마스크를포토레지스트에밀착시키는간단한방법으로,정밀하고 재현성있게에어캡의크기를조절할수있다.
[92] 관계식 3을만족하도록，광마스크를포토레지스트막상에정렬한후，상술한 바와같이,적어도 90mJ/cm2이상의광량 (dose)으로광을조사하여노광이수행될 수있다.
[93] 이때,조사되는광은자외선 (UV)일수있으며 , lOnm내지 500nm의파장대역의 자외선일수있다.구체적으로조사되는광은그중심파장이 300mn내지
500nm에위치할수있으며，보다구체적으로중심파장이 350내지 380nm, 400 내지 420nm및 /또는 420내지 450nm에위치할수있다.즉，본발명의일 실시예에따른제조방법은종래포토리소그래피공정에서통상적으로사용되는 I-line, H-line및 /또는 G-line의파장을포함하는자외선을이용하여노광이 수행될수있다.또한，노광단계는포토리소그래피공정에서통상적으로 사용되는광학수단들을이용하여광의조사가이루어질수있다.이는，본 발명에따른포토리소그래피방법이，광마스크이외에종래포토리소그래피 공정에서통상적으로사용되는포토레지스트및노광장치등을그대로이용할 수있기때문이다.
[94] 현상단계는포토리소그래피공정에서통상적으로사용하는현상액및
현상방법을통해이루어질수있다.포지티브형포토레지스트를사용한구체적 일예로，현상단계는노광에의해화학적특성이변화된감광성수지부분을 녹여제거하는용매를함유하는현상액을이용하여,화학적특성이변화된 감광성수지부분을제거함으로써이루어질수있다.이때,상술한바와같이， 현상시간을조절하여，단층내지다층고리현상의포토레지스트패턴을제조할 수있다.
[95] 본발명의일실시예에따른포토리소그래피방법에있어，상술한노광및 현상이이루어진후，기재에의불순물주입,기재의식각또는기재상물질 증착과같은후속공정이이루어질수있음은물론이며，후속공정이수행된후， 물리적또는화학적으로기재에잔류하는 (현상에의해잔류하는)
포토레지스트를제거하는단계가더수행될수있다.잔류하는포토레지스트의 제거는포토리소그래피공정에서현상된포토레지스트의제거를위해 통상적으로사용하는물질및방법을이용하여수행될수있음은물론이다.
[96] 도 1은본발명의제조방법으로제조된포토레지스트패턴을관찰한주사전자 현미경사진이다.
[97] 상세하게,평판형태의석영을투명기재로하여,투명기재의일면에높이가 lOOrnn이며반경이 500mn인 Cr판 (평판형금속닷)이 ΙΟμηι간격으로규칙적으로 배열형성되고, lOOnm의갭 (에어갭)이형성되도록돌출부가형성된광마스크를 이용하였다.실리콘웨이퍼인기재상 420nm두께 (관계식 1에서 m=4)의 포지티브포토레지스트막 (S1805)을형성한후,광마스크를포토레지스트막에 밀착정렬하고, 365nm의자외선을 101mJ/cm2의광량 (dose)으로조사하여노광을 수행하고，이후， 160초동안현상 (AZ300MIF)하여제조된포토레지스트패턴을 관찰한주사전자현미경사진이다.
[98] 도 2는제조된고리형포토레지스트패턴을원자간력현미경 (AFM;Atomic Force Microscope)으로관찰한결과를도시한도면이다.
[99] 도 1및도 2를통해알수있듯이，고가의 PSM이아닌，단지편평한판형태의 투명기재에평판형금속닷이형성된마스크를이용하여,속이빈고리형태로 포토레지스트가패턴화됨을알수있으며，외경이 1.86μηι이며，고리의폭이 667nm인단층의미세고리형패턴이제조됨을알수있다.
[100] 도 3은도 1에서관찰한포토레지스트패턴과동일한방법으로제조하되, 현상을 62초동안수행하여제조된포토레지스트패턴을관찰한
주사전자현미경사진이며，도 4는도 1에서관찰한포토레지스트패턴과동일한 방법으로제조하되,현상을 17초동안수행하여제조된포토레지스트패턴을 관찰한주사전자현미경사진이다.
[101] 도 3및도 4에서알수있듯이，본발명의제조방법으로，동심구조를가지며， 상부에위치할수록고리의외경이작아지는，다층의고리패턴이제조됨을알수 있다.
[102] 또한，도 1，도 3내지도 4에도시한바와같이,다층고리구조로노광영역이 형성되도록노광을수행한후，단지현상시간을조절하여，단층, 2층또는 3층 구조의고리형패턴이제조됨을알수있다.
[103] 나아가，도 4에서알수있듯이，직경이 lOOOnm인평판형금속닷이형성된광 마스크를이용하여，외경이 955nm및외경이 805nm인，평판형금속닷보다도 크기가작은고리패턴이제조됨을알수있다.
[104] 도 1에서관찰한포토레지스트패턴과동일한방법으로제조하되,조사되는 광의광량이 l UmJ/cm2가되도록노광을수행한결과，현상시간과무관하게 단층고리형태의포토레지스트패턴이제조되는것을확인하였다.
[105] 또한， m=3.5가되도록포토레지스트막의두께를조절하는경우，도 1,도 3및 도 4에서관찰한포토레지스트패턴과동일한방법으로노광및현상을 수행하였으나，고리형패턴이제조되지않음을확인하였다.
[106] 이상과같이본발명에서는특정된사항들과한정된실시예및도면에의해 설명되었으나이는본발명의보다전반적인이해를돕기위해서제공된것일 뿐，본발명은상기의실시예에한정되는것은아니며，본발명이속하는 분야에서통상의지식을가진자라면이러한기재로부터다양한수정및변형이 가능하다.
[107] 따라서，본발명의사상은설명된실시예에국한되어정해겨서는아니되며， 후술하는특허청구범위뿐아니라이특허청구범위와균등하거나등가적변형 6 있는모든것들은본발명사상의범주에속한다고할것이다.
[108]
[109]

Claims

청구범위
a)기판상하기관계식 1을만족하는포토레지스트막을형성하는 단계;및
b)투명기재및투명기재의광의출사면에접하여형성된평판형 금속닷 (plate-type metal dot)을포함하는광마스크를이용하여 , 포토레지스트막을노광하고，노광된포토레지스트막을 현상하여，고리형상의포토레지스트패턴을제조하는단계; 를포함하는포토리소그래피방법. '
(관계식 1)
D=m*(X/2n)
(D는포토레지스트막의두께이며， n은포토레지스트의
굴절률이며 , λ는노광시조사되는광의파장이며， m은 1이상의 자연수이다)
제 1항에있어서，
상기광마스크는하기관계식 2를만족하며，
상기광마스크와상기포토레지스트막간의간격은하기관계식
3을만족하는포토리소그래피방법 .
(관계식 2)
150nm < R < 1.5μπι
(관계식 2에서， R은평판형금속닷의반지름이다)
(관계식 3)
50 < Gap < 200 nm
(관계식 3에서, Gap는광마스크와포토레지스트막간의이격 거리이다)
제 1항에있어서，
상기평판형금속닷의금속은 Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt및 Au를포함하는전이금속; Al, Ga, In, Tl, Sn, Pb및 Bi를포함하는 전이후금속;및 Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs및 Ba을포함하는 금속;에서하나이상선택되는포토리소그래피방법.
제 I항에있어서,
상기노광시조사되는광은자외선 (UV)이며， 90내지 110 mJ/cm2 의광량으로조사되는포토리소그래피방법.
제 1항내지제 4항중어느한항에있어서，
상기포토레시스트패턴은단층고리형상또는둘이상의고리가 적층된다층고리형상이며,상기다층고리형상의각고리는 동심구조를가지며，광조사방향으로의투사 (projection)이미지 상,상부고리가하부고리내부에위치하는포토레지스트방법 . [청구항 6] 제 5항에있어서，
상기다층고리형상의상부고리외경은상기금속닷의직경보다 작은포토레지스트방법 .
[청구항 7] 제 5항에있어서，
상기단층고리형상또는다층고리형상의포토레시스트패턴은 상기노광시조사되는광의광량 (dose)및현상시간중적어도 하나이상선택되는인자에의해조절되는포토레지스트방법ᅳ [청구항 8] 제 1항내지제 4항중어느한항의방법을이용하여제조된
포토레지스트패턴. ,
PCT/KR2015/005768 2015-01-15 2015-06-09 포토리소그래피 방법 Ceased WO2016114455A1 (ko)

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