Method of fabrication and control of nano-structure array by angle-resolved exposure in proximity-field nano patterning
11837470 · 2023-12-05
Assignee
- Samsung Electronics Co., Ltd. (Suwon-si, KR)
- Korea Advanced Institute Of Science And Technology (Daejeon, KR)
Inventors
Cpc classification
H01L29/66439
ELECTRICITY
H01L29/775
ELECTRICITY
H01L29/42392
ELECTRICITY
G03F7/201
PHYSICS
H01L29/78696
ELECTRICITY
International classification
H01L21/027
ELECTRICITY
H01L21/02
ELECTRICITY
H01L29/06
ELECTRICITY
H01L29/423
ELECTRICITY
H01L29/66
ELECTRICITY
H01L29/775
ELECTRICITY
Abstract
A method for fabricating a nano-structure includes: providing a phase mask having an uneven lattice structure to contact a photoresist film; exposing the photoresist film to a light through the phase mask such that the light is obliquely incident on a surface of the photoresist film; and developing the photoresist film to form a nano-structure.
Claims
1. A method for fabricating a nano-structure, the method comprising: providing a phase mask having an uneven lattice structure to contact a photoresist film; exposing the photoresist film to a light through the phase mask such that the light is obliquely incident on a surface of the photoresist film; and developing the photoresist film to form a nano-structure, wherein an incidence angle of the light on the photoresist film satisfies the following formula:
2. The method of claim 1, wherein the uneven lattice structure has an one-dimensional lattice structure including protrusions extending in a direction, and wherein the nano-structure includes a plurality of channels extending in a horizontal direction.
3. The method of claim 2, wherein lines connecting four channels adjacent to each other in a cross-sectional view of the photoresist film form a rectangular shape.
4. The method of claim 1, wherein the phase mask has a prism shape including an inclined surface with the uneven lattice structure, and wherein the photoresist film is disposed on the inclined surface so that the light is irradiated on the photoresist film through a lower surface of the prism shape.
5. The method of claim 1, wherein the phase mask includes polydimethylsiloxane (PDMS).
6. The method of claim 1, wherein the phase mask includes a lattice portion including the uneven lattice structure and a film portion combined with the lattice portion, and wherein the lattice portion has a modulus greater than the film portion.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The patent application file contains at least one drawing sheet executed in color. Copies of this patent application publication with the color drawings will be provided by the Office upon request and payment of the necessary fee.
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
(13)
DETAILED DESCRIPTION OF THE EMBODIMENTS
(14) Various embodiments will be described more fully hereinafter with reference to the accompanying drawings. These embodiments are all example embodiments of the inventive concept. The inventive concept may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided such that this description will be thorough and complete, and will fully convey the scope of the inventive concept to those skilled in the art. In the drawings, the sizes and relative sizes of layers and regions may be exaggerated for clarity.
(15) It will be understood that when an element or layer is referred to as being “on,” “connected to” or “coupled to” another element or layer, it can be directly on, connected or coupled to the other element or layer or intervening elements or layers may be present. In contrast, when an element is referred to as being “directly on,” “directly connected to” or “directly coupled to” another element or layer, there are no intervening elements or layers present. Like numerals refer to like elements throughout. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items.
(16) It will be understood that, although the terms first, second, third etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another region, layer or section. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the invention.
(17) The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms “a,” “an” and “the” are intended to include a plurality of forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises” and/or “comprising,” when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
(18) Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
(19)
(20) Referring to
(21) The base substrate 100 may include silicon, quartz, sapphire, a polymer, a metal or a combination thereof. The polymer may include polymethylmethacrylate (PMMA), polyethylene terephthalate (PET), polycarbonate (PC), polyimide (PI), polyamide (PA), polypropylene (PP) or a combination thereof.
(22) A photoresist composition may be coated on the base substrate 100, and may be soft-baked, for example, at about 50° C. to about 100° C. to form the photoresist film 110. A time for soft-baking may be adjusted as desired. For example, the soft-baking may be performed for about 5 minutes to about 3 hours.
(23) The photoresist composition for forming the photoresist film 110 may include an organic-inorganic hybrid material, hydrogel, a phenolic resin, an epoxy resin, or the like, which may be cross-linked by light exposure. For example, SU-8 series, KMPR series, ma-N 1400, which are from MicroChem, NR5-6000p from Futurrex, or the like may be used for the photoresist composition.
(24) According to an embodiment, the photoresist film 110 may be patterned by a PnP method. Referring to
(25) In the PnP process, the photoresist film 110 may be patterned according to a periodic 3D distribution of a light passing through the phase mask 120. A light passing through the phase mask 120 is periodically 3D-distributed by interference effect. Thus, the photoresist film 110 may be three-dimensionally exposed (3D-exposed) to a light. The phase mask 120 may have a convexo-concave lattice structure formed on a surface thereof, through which a light passes. The phase mask 120 may include a flexible elastomer material. When the phase mask 120 contacts the photoresist film 110, the phase mask 120 may spontaneously adhere to or conformal-contact a surface of the photoresist film 110 by a Van der Waals force.
(26) When a laser beam having a wavelength similar to a period of the lattice-structure of the phase mask 120 is irradiated onto the phase mask 120, a 3D-distributed light may be formed by a Talbot effect. When the photoresist film 110 is formed from a negative-tone photoresist composition, cross-linking of a resin may selectively occur in a portion where light intensity is relatively high by constructive interference, and may hardly occur in a remaining portion where light intensity is relative low. Thus, the remaining portion, which is barely or not light-exposed, may be removed in a developing process. As a result, a nano-structure having channels arranged with a period of hundreds of nanometers to micrometers may be obtained. After the developing process, the photoresist film may be dried.
(27) According to an embodiment, the phase mask 120 used in the PnP process may include a material such as polydimetylsiloxane (PDMS), polyurethane acrylate (PUA), perfluoropolyether (PFPE), or the like.
(28) An exposing dose energy of the light-exposure process may be about 10 mJ/cm.sup.2 to about 300 mJ/cm.sup.2. The light used for the light-exposure process may have a wavelength corresponding to a ultraviolet (UV) ray. For example, a laser beam having a wavelength of about 300 nm to about 400 nm may be used. However, the embodiments are not limited thereto, and lights having various wavelengths may be used for the light-exposure process.
(29) According to an embodiment, a light such as a laser beam may be obliquely incident on a surface of the photoresist film 110. Here, the obliquely incident light may be a light beam, ray or component having a maximum intensity in the light output from a light source or a light-exposure apparatus. An incidence angle θ1 of the light may be determined depending on a shape of a desired nano-structure.
(30) According to an embodiment, the photoresist film 110 and the phase mask 120 may be inclined by a same angle as the incidence angle θ1 of the light so that a vertically downward-directed light may enter a surface of the photoresist film 110 with the incidence angle θ1.
(31) Referring to
(32) According to an embodiment, the lattice portion 124 may have a modulus greater than the film portion 122 so that a profile of the uneven lattice structure may be improved while maintaining flexibility of the phase mask 120. According to an embodiment, the film portion 122 and the lattice portion 124 may include PDMS. The lattice portion 124 may include PDMS with increased hard segments therein to have a modulus higher than the film portion 122. The PDMS with increased hard segments may be obtained by reaction of PDMS having a hydroxyl end group with diisocyanate and a chain extender (diol or diamine).
(33) According to an embodiment, diffraction of a light passing through the phase mask 120 may be adjusted depending on a combination of an incidence angle of the light, a wavelength of the light, a period P (pitch of protrusions) of the lattice portion 124 and a depth D of the lattice portion 124 to form a nano-structure having channels with a desired arrangement.
(34) For example, in order to form a nano-structure in which lines connecting four adjacent channels in a cross-sectional view form a substantially rectangular shape, an incidence angle θ1 of a light incident on an upper surface (contact surface) of the photoresist film 110 may be about 17° to about 20°. Furthermore, a wavelength of the light may be about 350 nm to about 370 nm. Furthermore, a period P of the lattice portion 124 may be about 350 nm to about 500 nm. Furthermore, a depth D of the lattice portion 124 may be about 100 nm to about 300 nm.
(35) For example, the light-exposed photoresist film 110 may be baked at about 50° C. to about 100° C. to form the nano-structure. A time for baking may be adjusted as desired. For example, the baking may be performed for about 5 minutes to about 30 minutes.
(36) Referring to
(37) Referring to
(38) The developer may include propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, diacetone alcohol, tetramethylammonium hydroxide (TMAH), a developer solution for Su-8, or the like.
(39) After developed, the photoresist film 110 may be rinsed by deionized water, an alcohol such as ethanol or isopropyl alcohol, or the like to obtain the nano-structure.
(40) According to the present embodiment, a nano-structure, which may not be obtained by a conventional PnP process, may be obtained by adjusting an incidence angle of a light incident on a photoresist film.
(41) According to the present embodiment, a photoresist film may be inclined to adjust an incidence angle of a light vertically incident on the photoresist film. However, embodiments are not limited thereto, and various other methods may be used for adjusting the incidence angle.
(42) For example,
(43)
(44) Referring to
(45) Referring to
(46) Referring to
(47) Referring to
(48)
(49) Referring to
(50) For example, the photoresist film 110 or the mold 400 may be heated, or an organic solvent such as ethanol may be provided on a pressed surface of the photoresist film 110, in order to effectively perform the imprinting process.
(51) According to an embodiment, the photoresist film 110 may have a lattice structure formed on a surface thereof. Thus, a PnP process may be performed without a phase mask.
(52) Referring to
(53) According to an embodiment, referring to
(54) According to an embodiment, referring to
(55) The conventional PnP methods may be able to form only a body-centered-cubic (BCC) structure, a body-centered-tetragonal (BCT) structure and a diamond-like structure as a 3D nano-structure, and a hexagonal-arranged nano-channel structure as a 2D nano-structure. This is because, in the conventional PnP method, a light source is directed to a surface of a photoresist film such that a light from the light source is vertically incident on the photoresist film through a phase mask, and thus, the light has symmetrical distribution of diffraction intensities and diffraction directions. However, the above embodiments may enable formation of different structures that may not be obtained by the conventional PnP methods.
(56) Further, the above embodiments may enable improved process suitability and nano-device performance. For example, a nano-structure obtained from the above embodiments may be used for forming channels of a gate-all-around field-effect transistor (GAA FET). For example, channels (pores) of the nano-structure may be filled with a channel material such as a semiconductor material by a deposition method such atomic layer deposition (ALD) or the like to form electric channels of the GAA FET. After the electric channels are formed, the nano-structure may be entirely or partially removed, and a space obtained from the removal of the nano-structure may be filled with other materials, for example, a conductive material, an insulating material or a semiconductor material.
(57) Furthermore, an arrangement of channels, which may be obtained by the above embodiments, is not limited to a rectangular arrangement, and various other arrangements may be obtained as desired.
(58)
(59) In
(60)
(61) The simulation was performed such that a wavelength of a light was 355 nm, a period of a lattice structure was 400 nm, a depth of the lattice structure was 200 nm, a refractive index of a phase mask PDMS was 1.4, and a refractive index of a photoresist film was 1.66.
(62) Referring to
(63) Based on the EFC analysis and the simulation, a light incidence angle for forming channels arranged in a rectangular shape may satisfy the following Formula 1.
(64)
(65) In Formula 1, n.sub.i is a refractive index of a medium, through which a light passes before entering a photoresist film. n.sub.pr is a refractive index of the photoresist film. λ is a wavelength of the light in vacuum. P is a period of a lattice structure (period of protrusions). θ.sub.i is an incidence angle of the light on the photoresist film.
(66) Thus, when a phase mask having the lattice structure is used for forming a 3D distribution of a light, n.sub.i may be a refractive index of the phase mask.
(67) Furthermore, as illustrated in
COMPARATIVE EXAMPLE
(68) A composition for a high modulus PDMS was spin-coated on a silicon substrate having a lattice pattern, and reaction for cross-linking progressed at 65° C. for 10 minutes. A composition for a low modulus PDMS was provided on the high modulus PDMS layer, and reaction for cross-linking progressed for at least 24 hours. The cured PDMS was separated from the silicon substrate to obtain a phase mask.
(69) A photoresist composition (trade name: SU-8, manufactured by MicroChem) was spin-coated on a glass substrate, and heated on a hot plate at 50° C. to 100° C. for 60 minutes to form a photoresist film. Thereafter, the phase mask was disposed on the photoresist film.
(70) Thereafter, a laser beam having a wavelength of 365 nm was irradiated on the photoresist film through the phase mask with 10 mJ/cm.sup.2 to 40 mJ/cm.sup.2, and a post-exposure baking was performed at 50° C. to 65° C. for 5 minutes to 15 minutes. Thereafter, the photoresist film was dipped in a PGMEA solution for at least 20 minutes, and supercritical-dried by using carbon dioxide at −8° C. to 45° C. under 15 psi to 1,300 psi to obtain a nano-structure.
EXAMPLE 1
(71) A silicon substrate having a lattice pattern with a high modulus PDMS layer spin-coated thereon was disposed in a container to be inclined by a desired angle. A composition for a low modulus PDMS was provided in the container to surround the silicon substrate and the high modulus PDMS layer. After the composition was cured, the silicon substrate combined with PDMS was taken out of the container and cut to form a phase mask with a jig shape having an inclined surface by 20°.
(72) A photoresist composition (SU-8) was spin-coated on a glass substrate, and heated on a hot plate at 50° C. to 100° C. for 60 minutes to form a photoresist film. The photoresist film was disposed on the inclined surface of the phase mask, and exposed to a light through a same method as Comparative Example 1.
(73)
(74) Referring to
(75)
(76) The simulation was performed based on the EFC analysis illustrated in
(77) Referring to
(78) As explained in the above, a nano-structure, which may not be obtained by a conventional PnP method, may be obtained according to the above embodiments. The above embodiments may use various light source such as g-line emitting a light with a wavelength of about 345 nm, h-line emitting a light with a wavelength of about 405 nm, i-line emitting a light with a wavelength of about 365 nm, deep UV emitting a light with a wavelength equal to or less than about 280 nm, extreme UV emitting a light with a wavelength equal to or less than about 120 nm or the like.
(79) A method for fabricating a nano-structure may be used for manufacturing various nano-devices such as a semiconductor device, a sensor, a capacitor or the like.
(80) The foregoing is illustrative of example embodiments and is not to be construed as limiting thereof. Although a few embodiments have been described, those skilled in the art will readily appreciate that many modifications are possible in the embodiments without materially departing from the novel teachings and advantages of the present inventive concept. Accordingly, all such modifications are intended to be included within the scope of the present inventive concept as defined in the claims. Therefore, it is to be understood that the foregoing is illustrative of various embodiments and is not to be construed as limited to the specific embodiments disclosed, and that modifications to the disclosed embodiments, as well as other embodiments, are intended to be included within the scope of the appended claims.