Alternating self-assembling morphologies of diblock copolymers controlled by variations in surfaces
Methods for fabricating sublithographic, nanoscale microstructures arrays including openings and linear microchannels utilizing self-assembling block copolymers, and films and devices formed from these methods are provided. In some embodiments, the films can be used as a template or mask to etch openings in an underlying material layer.
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Embodiments of the invention relate to methods of fabricating nanostructures by use of thin films of self-assembling block copolymers, and devices resulting from those methods.
BACKGROUND OF THE INVENTIONAs the development of nanoscale mechanical, electrical, chemical and biological devices and systems increases, new processes and materials are needed to fabricate nanoscale devices and components. Optical lithographic processing methods are not able to accommodate fabrication of structures and features at the nanometer level. The use of self assembling diblock copolymers presents another route to patterning at nanometer dimensions. Diblock copolymer films spontaneously assembly into periodic structures by microphase separation of the constituent polymer blocks after annealing, for example by thermal annealing above the glass transition temperature of the polymer or by solvent annealing, forming ordered domains at nanometer-scale dimensions. Following self assembly, one block of the copolymer can be selectively removed and the remaining patterned film used, for example, as an etch mask for patterning nanosized features into the underlying substrate. Since the domain sizes and periods (Lo) involved in this method are determined by the chain length of a block copolymer (MW), resolution can exceed other techniques such as conventional photolithography, while the cost of the technique is far less than electron beam (E-beam) lithography or EUV photolithography, which have comparable resolution.
The film morphology, including the size and shape of the microphase-separated domains, can be controlled by the molecular weight and volume fraction of the AB blocks of a diblock copolymer to produce lamellar, cylindrical, or spherical morphologies, among others. For example, for volume fractions at ratios greater than about 80:20 of the two blocks (AB) of a diblock polymer, a block copolymer film will microphase separate and self-assemble into a periodic spherical domains with spheres of polymer B surrounded by a matrix of polymer A. For ratios of the two blocks between about 60:40 and 80:20, the diblock copolymer assembles into periodic cylindrical domains of polymer B within a matrix of polymer A. For ratios between about 50:50 and 60:40, lamellar domains or alternating stripes of the blocks are formed. Domain size typically ranges from 5-50 nm.
Researchers have demonstrated the ability to chemically differentiate a surface such that some areas are preferentially wetting to one domain of a block copolymer and other areas are neutral wetting to both blocks. Periodic cylindrical structures have been grown in parallel and perpendicular orientations to substrates within trenches by thermal annealing cylindrical-phase block copolymers. A primary requirement for producing perpendicular cylinders is that the trench floor must be non-preferential or neutral wetting to both blocks of the copolymer. For producing parallel-oriented half-cylinders, the trench floor must by preferentially wetting by the minor copolymer block.
A film composed of periodic hexagonal close-packed cylinders, for example, can be useful in forming an etch mask to make structures in an underlying substrate for specific applications such as magnetic storage devices. However, many applications require a more complex layout of elements for forming contacts, conductive lines and/or other elements such as DRAM capacitors.
Embodiments of the invention are described below with reference to the following accompanying drawings, which are for illustrative purposes only. Throughout the following views, the reference numerals will be used in the drawings, and the same reference numerals will be used throughout the several views and in the description to indicate same or like parts.
The following description with reference to the drawings provides illustrative examples of devices and methods according to embodiments of the invention. Such description is for illustrative purposes only and not for purposes of limiting the same.
In the context of the current application, the term “semiconductor substrate” or “semiconductive substrate” or “semiconductive wafer fragment” or “wafer fragment” or “wafer” will be understood to mean any construction comprising semiconductor material, including but not limited to bulk semiconductive materials such as a semiconductor wafer (either alone or in assemblies comprising other materials thereon), and semiconductive material layers (either alone or in assemblies comprising other materials). The term “substrate” refers to any supporting structure including, but not limited to, the semiconductive substrates, wafer fragments or wafers described above.
“Lo” is the inherent pitch (bulk period or repeat unit) of structures that self assemble upon annealing from a self-assembling (SA) block copolymer or a blend of a block copolymer with one or more of its constituent homopolymers.
In embodiments of the invention, processing conditions utilize graphoepitaxy techniques that use topographical features, e.g., the sidewalls and ends of trenches, as constraints to induce the formation and registration of polymer domains of cylindrical-phase diblock copolymers in one dimension (e.g., hexagonal close-packed (honeycomb) array or single row of perpendicular cylinders) and chemically or structurally (topographically) differentiated trench floors to provide a wetting pattern to control orientation of the microphase separated and self-assembling cylindrical domains in a second dimension (e.g., parallel lines of half-cylinders or perpendicular-oriented cylinders). The trench floors are structured or composed of surface materials to provide a neutral wetting surface or preferential wetting surface to impose ordering on a block copolymer film that is then cast on top of the substrate and annealed to produce desired arrays of nanoscale cylinders.
Embodiments of the invention provide a means of generating self-assembled diblock copolymer structures wherein perpendicular cylinders are formed in some trenches and parallel-oriented half-cylinders are formed in other trenches. Control of the orientation of the cylinders is provided by the nature of the trench floor surface. Graphoepitaxy is used to provide parallel lines of half-cylinders, hexagonal close-packed arrays of perpendicular cylinders, or a single row of perpendicular cylinders within lithographically defined trenches. A desired pattern of cylinders on a substrate, e.g., a wafer, can be prepared by providing trenches having walls that are selective to one polymer block of a block copolymer and a floor composed either of a material that is block-sensitive or preferentially wetting to one of the blocks of the block copolymer in trenches where lines of parallel half-cylinders are desired, or a material that is neutral wetting to both blocks in trenches where an array of perpendicular cylinders are desired. Embodiments of the invention can be used to pattern lines and openings (holes) in the same patterning step at predetermined locations on a substrate.
Embodiments of the invention of methods for fabricating arrays of cylinders from thin films of cylindrical-phase self assembling (SA) block copolymers are described with reference to the figures. As shown in
The trenches can be formed using a lithographic tool having an exposure system capable of patterning at the scale of Lo (10-100 nm). Such exposure systems include, for example, extreme ultraviolet (EUV) lithography, dry lithography (e.g., 248 nm, 193 nm), immersion lithography (e.g., 193 nm), and electron beam lithography, as known and used in the art. Conventional photolithography can attain about 58 nm features. A method called “pitch doubling” or “pitch multiplication” can also be used for extending the capabilities of photolithographic techniques beyond their minimum pitch, as described, for example, in U.S. Pat. No. 5,328,810 (Lowrey et al.), U.S. Pat. No. 7,115,525 (Abatchev, et al.), US 2006/0281266 (Wells) and US 2007/0023805 (Wells), the disclosures of which are incorporated by reference herein. Briefly, a pattern of lines is photolithographically formed in a photoresist layer overlying a layer of an expendable material, which in turn overlies a substrate, the expendable material layer is etched to form placeholders or mandrels, the photoresist is stripped, spacers are formed on the sides of the mandrels, and the mandrels are then removed leaving behind the spacers as a mask for patterning the substrate. Thus, where the initial photolithography formed a pattern defining one feature and one space, the same width now defines two features and two spaces, with the spaces defined by the spacers. As a result, the smallest feature size possible with a photolithographic technique is effectively decreased down to about 30 nm or more.
The trenches 14a-14c are structured with opposing sidewalls 16, opposing ends 18, a floor 20, a width (wt), a length (lt) and a depth (Dt). Trench 14c is also structured with the trench ends 18 angled to the sidewalls 16, for example, at an about 60° angle, and in some embodiments, the trench ends are slightly rounded. Portions of the material layer 12 form a spacer 12a between the trenches.
The trench sidewalls, edges and floors influence the self-assembly of the polymer blocks and the structuring of the array of nanostructures within the trenches. The boundary conditions of the trench sidewalls 16 impose order in the x-direction (x-axis) and the ends 18 impose order in the y-direction (y-axis) to impose a structure wherein each trench contains n number of features (i.e., cylinders). Other factors that influence the formation and alignment of elements within the trench include the width (wt) of the trench, the formulation of the block copolymer to achieve the desired pitch (Lo), the thickness (t) of the block copolymer film, and the wetting nature of the trench surfaces.
Entropic forces drive the wetting of a neutral wetting surface by both blocks, and enthalpic forces drive the wetting of a preferential-wetting surface by the preferred block (e.g., the minority block). The trench sidewalls 16 and ends 18 are structured to be preferential wetting such that upon annealing, the preferred block of the block copolymer will segregate to the sidewalls and edges of the trench to assemble into a thin (e.g., ¼ pitch) interface (wetting) layer, and will self-assemble to form cylinders in the center of a polymer matrix within each trench, the cylinders being in a perpendicular orientation on neutral wetting floor surfaces and half-cylinders in a parallel orientation in relation to preferential wetting floor surfaces.
As illustrated in
As shown in
For example, a block copolymer having a 35-nm pitch (Lo value) deposited into a 75-nm wide trench having a neutral wetting floor will, upon annealing, result in a zigzag pattern of 35-nm diameter perpendicular cylinders that are offset by a half distance for the length (lb) of the trench, rather than a single line of perpendicular cylinders aligned with the sidewalls down the center of the trench. As the Lo value of the copolymer is increased, for example, by forming a ternary blend by the addition of both constituent homopolymers, there is a shift from two rows to one row of the perpendicular cylinders within the center of the trench.
In some embodiments, the substrate 10 can be a material that is inherently preferential wetting to one of the blocks, and a neutral wetting surface layer 22 can be provided by applying a neutral wetting polymer (e.g., a neutral wetting random copolymer) onto the substrate 10 and then selectively removing the layer 22 to expose portions of the preferential wetting surface of the substrate. For example, in the use of a poly(styrene-block-methyl methacrylate) block copolymer (PS-b-PMMA), a random PS:PMMA copolymer (PS-r-PMMA) which exhibits non-preferential or neutral wetting toward PS and PMMA can be applied. The polymer layer can be affixed by grafting (on an oxide substrate) or by cross-linking (any surface) using UV radiation or thermal processing.
As shown in
In another embodiment depicted in
For example, a neutral wetting polymer (NWP) such as a random copolymer of polystyrene (PS), polymethacrylate (PMMA) with hydroxyl group(s) (e.g., 2-hydroxyethyl methacrylate (P(S-r-MMA-r-HEMA)) (e.g., about 58% PS) can be can be selectively grafted to a material layer (e.g., an oxide floor) as a layer 22″ of about 5-10 nm thick by heating at about 160° C. for about 48 hours (
A surface that is neutral wetting to PS-b-PMMA can also be prepared by spin coating a blanket layer of a photo- or thermally cross-linkable random copolymer such as a benzocyclobutene- or azidomethylstyrene-functionalized random copolymer of styrene and methyl methacrylate (e.g., poly(styrene-r-benzocyclobutene-r-methyl methacrylate (PS-r-PMMA-r-BCB)). For example, such a random copolymer can comprise about 42% PMMA, about (58-x) % PS and x % (e.g., about 2-3%) of either polybenzocyclobutene or poly(para-azidomethylstyrene)). An azidomethylstyrene-functionalized random copolymer can be UV photo-crosslinked (e.g., 1-5 MW/cm^2 exposure for about 15 seconds to about 30 minutes) or thermally crosslinked (e.g., at about 170° C. for about 4 hours) to form a crosslinked polymer mat as a neutral wetting layer 22″. A benzocyclobutene-functionalized random copolymer can be thermally cross-linked (e.g., at about 200° C. for about 4 hours or at about 250° C. for about 10 minutes). The layer 22″ can be globally photo- or thermal-crosslinked (
In other embodiments, as illustrated in
Referring now to
In other embodiments, a neutral wetting layer (22) can be provided by grafting a random copolymer such as PS-r-PMMA selectively onto an H-terminated silicon substrate (e.g., 20′″ floor) in
In other embodiments, a layer of a preferential wetting material can be applied onto the surface of the substrate exposed as the floors of trenches 14b. For example, a layer of oxide or silicon nitride, etc. can be deposited as a blanket layer into the trenches (e.g., as shown in
In yet another embodiment, the floors of the trenches can be made neutral or preferential wetting by varying the roughness of the surface of the trenches floor, as described, for example, in Sivaniah et al., Macromolecules 2005, 38, 1837-1849, and Sivaniah et al., Macromolecules 2003, 36, 5894-5896, the disclosure of which are incorporated by reference herein. A grooved or periodic grating-like substrate topography having a lateral periodicity and structure at or above a critical roughness value (e.g., qsR where qs=2π/λs, R is the (root-mean-square) vertical displacement of the surface topography about a mean horizontal plane, and λs is the lateral periodicity in the surface topography) can be provided to form a neutral wetting surface (e.g., trenches 14a, 14c) for formation of perpendicular cylinders (under conditions of a neutral wetting air surface). The floors of trenches 14b can be provided with a low surface roughness below the critical qsR, value for formation of parallel-oriented half-cylinders in those trenches. The critical roughness of the floor surface topography can also be adjusted according to the molecular weight of the block copolymer to achieve a perpendicular orientation of cylinders. The roughness of the substrate surface can be characterized using atomic force microscopy (AFM).
For example, as shown in
Referring now to
Referring now to
The copolymer material layer 28 is deposited into the trenches 14a-14c to a thickness (t) such that during an anneal, the capillary forces pull excess material (e.g., greater than a monolayer) into the trench. The resulting thickness of layer 28 in the trench is at about the Lo value of the copolymer material such that the copolymer film layer will self assemble upon annealing to form an array of cylindrical elements, for example, perpendicular cylindrical domains having a diameter at or about 0.5 Lo (e.g., about 20 nm) over the neutral wetting surface 22 of trenches 14a, 14c, and a single layer of lines of parallel-oriented half-cylinders with a diameter at or about 0.5 Lo over the preferential wetting floor 20 of trenches 14b. The film thickness can be measured, for example, by ellipsometry. Depending on the depth (Dt) of the trenches, the cast block copolymer material 28 can fill the trenches where the trench depth is about equal to Lo (Dt˜L0), or form a thinner film over the trench floor where the trench depth (Dt) is greater than Lo (Dt>L0) as depicted. A thin film of the copolymer material 28 generally less than Lo can be deposited on the spacers 12a, this material will not self-assemble, as it is not thick enough to form structures.
Although diblock copolymers are used in the illustrative embodiment, other types of block copolymers (i.e., triblock or triblock or multiblock copolymers) can be used. Examples of diblock copolymers include poly(styrene-block-methyl methacrylate) (PS-b-PMMA), polyethyleneoxide-polyisoprene, polyethyleneoxide-polybutadiene, polyethyleleoxide-polystyrene, polyetheleneoxide-polymethylmethacrylate, polystyrene-polyvinylpyridine, polystyrene-polyisoprene (PS-b-PI), polystyrene-polybutadiene, polybutadiene-polyvinylpyridine, and polyisoprene-polymethylmethacrylate, among others. Examples of triblock copolymers include poly(styrene-block methyl methacrylate-block-ethylene oxide). An example of a PS-b-PMMA copolymer material (Lo=35 nm) is composed of about 70% PS and 30% PMMA with a total molecular weight (Me) of 67 kg/mol, to form 20 nm diameter cylindrical PMMA domains in a matrix of PS.
The block copolymer material can also be formulated as a binary or ternary blend comprising a SA block copolymer and one or more homopolymers of the same type of polymers as the polymer blocks in the block copolymer, to produce blends that swell the size of the polymer domains and increase the Lo value of the polymer. The volume fraction of the homopolymers can range from 0 to about 40%. An example of a ternary diblock copolymer blend is a PS-b-PMMA/PS/PMMA blend, for example, 46K/21K PS-b-PMMA containing 40% 20K polystyrene and 20K poly(methylmethacrylate). The Lo value of the polymer can also be modified by adjusting the molecular weight of the block copolymer.
Optionally, ellipticity (“bulging”) can be induced in the structures by creating a slight mismatch between the trench and the spacer widths and the inherent pitch (Lo) of the block copolymer or ternary blend, as described, for example, by Cheng et al., “Self-assembled One-Dimensional Nanostructure Arrays,”, Nano Lett., 6 (9), 2099-2103 (2006), which then reduces the stresses that result from such mismatches.
Referring now to
The copolymer film can be thermally annealed to above the glass transition temperature of the component blocks of the copolymer material. For example, a PS-b-PMMA copolymer film can be annealed at a temperature of about 180-285° C. in a vacuum oven for about 1-24 hours to achieve the self-assembled morphology. The resulting morphologies of the block copolymer (i.e., perpendicular and parallel orientation of cylinders) can be examined, for example, using atomic force microscopy (AFM), transmission electron microscopy (TEM), and scanning electron microscopy (SEM).
The diameter of the perpendicular cylinders 30 and width of the half-cylinders 32 is generally about 0.5 Lo (e.g., about 20 nm). The center-to-center distance (pitch distance, p) between adjacent cylindrical domains within a trench is generally at or about Lo (e.g., about 40 nm for a 46/21 PS/PMMA block copolymer).
The hexagonal array of perpendicular cylinders 30 in trench 14c contains n rows of cylinders according to the width (wt) of the trench with the cylinders in each row being offset by about Lo (pitch distance (p) or center-to-center distance) from the cylinders in the adjacent rows. Each row contains “in” number of cylinders according to the length (lt) of the trench and the shape of the trench ends 18 (e.g., rounded, angled, etc.), with some rows having greater or less than m cylinders. The perpendicular cylinders 30 are spaced apart at a pitch distance (p) at or about Lo between cylinders in the same row and an adjacent row, and at a pitch distance (p) at or about Lo*cos(π/6) or about 0.866*Lo distance between two parallel lines where one line bisects the cylinders in a given row and the other line bisects the cylinders in an adjacent row.
The annealed and ordered film may then be treated to crosslink the polymer segments (e.g., the PS matrix 34) to fix and enhance the strength of the self-assembled polymer blocks within the trenches. The polymers can be structured to inherently crosslink (e.g., upon exposure to ultraviolet (UV) radiation, including deep ultraviolet (DUV) radiation), or one or both of the polymer blocks of the copolymer material can be formulated to contain a crosslinking agent. Non-ordered material outside the trenches (e.g., on spacers 12a) may then be removed.
For example, in one embodiment, the trench regions can be selectively exposed through a reticle (not shown) to crosslink only the self-assembled films within the trenches, and optionally, a wash can then be applied with an appropriate solvent (e.g., toluene) to remove non-crosslinked portions of the film 28 (e.g., on the spacers 12a). In another embodiment, the annealed films can be crosslinked globally, a photoresist layer can be applied to pattern and expose the areas of the film outside the trench regions (e.g., over the spacers 12a), and the exposed portions of the film can be removed, for example by an oxygen (O2) plasma treatment. In other embodiments, the spacers 12a are narrow in width, for example, a width (ws) of one of the copolymer domains (e.g., about Lo) such that the non-crosslinked block copolymer material 28 on the spacers is minimal and no removal is required. Material on the spacers 12a that is generally featureless need not be removed.
After annealing and the copolymer material is ordered, the minority polymer domains can be selectively removed from the films to produce a template for use in patterning the substrate 10. For example, as shown in
As shown in
Methods of the disclosure provide a means of generating self-assembled diblock copolymer structures where perpendicular cylinders preferentially form on some regions on a substrate and parallel cylinders form on other regions. In some embodiments, the desired orientation is controlled by the structure of the substrate (e.g., wafer) and/or the nature of the surface material. The methods provide ordered and registered elements on a nanometer scale that can be prepared more inexpensively than by electron beam lithography or EUV photolithography. The feature sizes produced and accessible by this invention cannot be prepared by conventional photolithography. Embodiments of the invention can be used to pattern lines and openings (holes) on a substrate in the same patterning step, thus eliminating processing steps compared to conventional process flows. The described methods can be readily employed and incorporated into existing semiconductor manufacturing process flows.
Although specific embodiments have been illustrated and described herein, it will be appreciated by those of ordinary skill in the art that any arrangement which is calculated to achieve the same purpose may be substituted for the specific embodiments shown. This application is intended to cover any adaptations or variations that operate according to the principles of the invention as described. Therefore, it is intended that this invention be limited only by the claims and the equivalents thereof. The disclosures of patents, references and publications cited in the application are incorporated by reference herein.
Claims
1. A method for fabricating nanoscale microstructures, comprising:
- forming a film comprising a cylindrical-phase block copolymer within a plurality of trenches to a thickness of about Lo, each trench having a width, length, sidewalls, ends and a floor, wherein the sidewalls and ends of the trenches are preferential wetting to a first block of the block copolymer, the floor of at least one trench is preferential wetting to said first block and the floor of another trench is neutral wetting to a second block of the block copolymer; and
- causing the block copolymer film to self-assemble to form perpendicularly-oriented cylindrical domains of the minority block of the block copolymer in a matrix of a majority block within trenches having said neutral wetting floor, and parallel-oriented half-cylindrical domains of the minority block in a matrix of the majority block within trenches having said preferential wetting floor.
2. The method of claim 1, wherein the at least one trench with a neutral wetting floor has a width of about 1.5*Lo to about 2*Lo.
3. The method of claim 1, wherein the at least one trench with a neutral wetting floor has a width of about nLo where n is an integer multiple greater than one.
4. The method of claim 3, wherein the ends of said trench are curved.
5. The method of claim 1, wherein the preferential wetting floor comprises a material selected from the group consisting of silicon (with native oxide), oxide, silicon nitride, silicon oxycarbide, silicon oxynitride, indium tin oxide, and methacrylate-based resists.
6. The method of claim 1, wherein the preferential wetting floor comprises a material having a surface roughness below a critical roughness for preferential wetting of the block copolymer.
7. The method of claim 6, wherein the preferential wetting floor induces a parallel orientation of cylindrical domains on said floor.
8. The method of claim 1, wherein the neutral wetting floor comprises a layer of a random copolymer.
9. The method of claim 1, wherein the neutral wetting floor comprises a layer of hydrogen-terminated silicon.
10. The method of claim 1, wherein the sidewalls and ends comprise a preferential wetting material selected from the group consisting of silicon (with native oxide), oxide, silicon nitride, silicon oxycarbide, silicon oxynitride, and methacrylate-based resists.
11. The method of claim 1, further comprising applying a preferential wetting material to the sidewalls and ends of the trenches.
12. The method of claim 1, further comprising crosslinking the self-assembled film.
13. The method of claim 1, further comprising, after causing the block copolymer film to self-assemble, selectively removing the minority polymer block to provide an array of perpendicular-oriented cylindrical openings and parallel-oriented half-cylindrical openings within the matrix of the majority polymer block.
14. The method of claim 13, further comprising extending the half-cylindrical openings to expose the floor of the trench.
15. A method for fabricating nanoscale microstructures, comprising:
- forming a material layer on a substrate, the material layer and the substrate being preferential wetting to a first block of a block copolymer;
- forming a plurality of trenches in the material layer, each trench having a width, length, sidewalls, ends and a floor, wherein the sidewalls and ends of the trenches are preferential wetting to said first block of the block copolymer;
- forming a neutral wetting layer on the floor of at least one trench wherein at least one other trench has a preferential wetting floor;
- forming a film comprising a cylindrical-phase block copolymer within the trenches to a thickness of about Lo; and
- annealing the block copolymer film to form perpendicularly-oriented cylindrical domains of a minority block of the block copolymer in a matrix of a majority block within trenches having the neutral wetting layer on the floor of said trench, and parallel-oriented half-cylindrical domains of the minority block in a matrix of the majority block within trenches having a preferential wetting floor.
16. A method for fabricating nanoscale microstructures, comprising:
- forming a material layer on a substrate;
- forming a plurality of trenches in the material layer, each trench having a width, length, sidewalls, ends and a floor, wherein the sidewalls and ends of the trenches are preferential wetting to a first block of a block copolymer;
- etching the floor of a first trench to a critical roughness for neutral wetting of said firstblock of the block copolymer;
- forming a preferential wetting layer on the floor of a second trench;
- forming a film comprising a cylindrical-phase block copolymer within the trenches to a thickness of about Lo; and
- annealing the block copolymer film to form perpendicularly-oriented cylindrical domains of a minority block of the block copolymer in a matrix of a majority block within the first trench having a neutral wetting floor, and parallel-oriented half-cylindrical domains of the minority block in a matrix of the majority block within the second trench having said preferential wetting layer on the floor of said trench.
17. The method of claim 16, wherein forming the preferential wetting layer comprises forming a layer of a material selected from the group consisting of oxide, nitride, silicon oxycarbide, silicon oxynitride, indium tin oxide, and a resist, selectively on the floor of the second trench.
18. A method for fabricating nanoscale microstructures, comprising:
- forming a neutral wetting layer on a substrate, the substrate being preferential wetting to a first block of a block copolymer and the neutral wetting layer being wetting to blocks a second block of the block copolymer;
- forming a material layer on the neutral wetting layer;
- forming a plurality of trenches in the material layer, each trench having a width, length, sidewalls, ends and a floor exposing the neutral wetting layer, wherein the sidewalls and ends of the trenches are preferential wetting to said first block of the block copolymer;
- removing the neutral wetting layer from the floor of at least one trench to expose the preferential wetting substrate as the floor of said trench wherein at least one trench retains the neutral wetting layer as the floor of said trench;
- forming a film comprising a cylindrical-phase block copolymer within the trenches to a thickness of about Lo; and
- annealing the block copolymer film to form perpendicularly-oriented cylindrical domains of a minority block of the block copolymer in a matrix of a majority block within said trenches having the neutral wetting layer as the floor of said trench, and parallel-oriented half-cylindrical domains of the minority block in a matrix of the majority block within trench having the preferential wetting substrate as the floor of said trench.
19. A method of etching a substrate, comprising:
- forming an etch mask, comprising: forming a film comprising a cylindrical-phase block copolymer within a plurality of trenches to a thickness of about Lo, each trench having a width, length, sidewalls, ends and a floor, wherein the sidewalls and ends of the trenches are preferential wetting to a first block of the block copolymer, and the floor of at least one trench is preferential wetting to said first block and the floor of another trench is neutral wetting to a second block of the block copolymer; annealing the film to cause the copolymer to self-assemble to form perpendicularly-oriented cylindrical domains of a minority block of the block copolymer in a matrix of a majority block within said trench having a neutral wetting floor, and parallel-oriented half-cylindrical domains of the minority block in a matrix of the majority block within said trench having a preferential wetting floor; and selectively removing the minority polymer block to provide an array of perpendicular-oriented cylindrical openings and parallel-oriented half-cylindrical openings within the matrix of the majority polymer block; and
- etching the substrate through the openings of the etch mask.
20. The method of claim 19, further comprising extending the half-cylindrical openings to expose the floor of the trench.
21. The method of claim 19, wherein the perpendicular-oriented cylindrical openings extend the length of at least one trench in a single array.
22. The method of claim 19, wherein the perpendicular-oriented cylindrical openings in at least one trench are in a hexagonal array.
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Type: Grant
Filed: Jun 12, 2007
Date of Patent: Feb 28, 2012
Patent Publication Number: 20080311347
Assignee: Micron Technology, Inc. (Boise, ID)
Inventors: Dan B. Millward (Boise, ID), Donald Westmoreland (Boise, ID), Gurtej Sandhu (Boise, ID)
Primary Examiner: Anita K Alanko
Attorney: Whyte Hirschboeck Dudek SC
Application Number: 11/761,589
International Classification: B44C 1/22 (20060101); B82B 3/00 (20060101); H01L 21/302 (20060101); B82Y 40/00 (20110101);