Extensions of self-assembled structures to increased dimensions via a “bootstrap” self-templating method
Methods for fabricating sublithographic, nanoscale arrays of openings and linear microchannels utilizing self-assembling block copolymers, and films and devices formed from these methods are provided. Embodiments of the invention use a self-templating or multilayer approach to induce ordering of a self-assembling block copolymer film to an underlying base film to produce a multilayered film having an ordered array of nanostructures that can be removed to provide openings in the film which, in some embodiments, 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 nanoscale arrays of micro-vias, microchannels and microstructures 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. Conventional optical lithographic processing methods are not able to accommodate fabrication of structures and features much below the 100 nm 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 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 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 a periodic hexagonal close-packed or honeycomb array of cylinders 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.
Diblock copolymer thin films of cylindrical and lamellar phases may both form striped phases relative to an interface. For cylindrical phase films, a striped pattern results from parallel cylinder orientation, while for lamellar phase films, a striped pattern results from perpendicular domain orientation. From a top down view, perpendicular-oriented lamellae and parallel-oriented cylinders appear similar, e.g., as parallel lines.
Graphoepitaxy techniques using defined topography such as trench edges have been used in an attempt to orient and order copolymer domains and control registration and alignment of the self-assembled blocks to form a desired pattern.
While the self-assembly of diblock copolymers of tightly controlled composition and polydispersity has been demonstrated as a method of preparing a variety of nanoscale, sub-lithographic structures, the necessity of casting only very thin films limits the dimensions of the structures, particularly in the z-axis direction (i.e., perpendicular to the substrate surface). Openings produced by selective etching and removal of polymer domains of the films may not achieve the required aspect ratio for critical dimensions of desired features.
It would be useful to provide a method of fabricating films of arrays of ordered nanostructures that overcome these problems.
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.
Processing conditions of embodiments of the invention use a graphoepitaxy technique utilizing the sidewalls of trenches as constraints to induce orientation and registration of a first film of a self assembling diblock copolymer to form an ordered array pattern registered to the trench sidewalls. The first polymer film is then used as a template or base layer for inducing the ordering of a subsequently deposited block copolymer film such that, upon annealing, the polymer domains orient and are registered to the underlying structures, resulting in a stacked double- or multi-layered structure with like polymer domains registered to each other. The procedure can be repeated as needed to achieve a desired structure pattern of a required dimension in the z-axis direction. In some embodiments, the desired patterned can be selectively etched by methods known in the art, and the resulting template structures can be used to prepare features within a substrate.
Steps in a method for fabricating thin films from self assembling (SA) block copolymers that define nanometer-scale linear array patterns according to embodiments of the invention are illustrated in
The method forms a multi-layer pattern within trenches by forming a polymer base film or template with ordered structures within the trenches for inducing the ordering of an overlying lamellar phase block copolymer film such that the lamellar domains are oriented perpendicularly and registered to the underlying assembled domains of the base film.
The base layer within the trenches can be formed from a lamellar-phase block copolymer film, which upon annealing forms a registered lamellar array of alternating polymer-rich blocks that extend the length and are oriented parallel to the sidewalls and perpendicular to the floor of the trenches. In other embodiments, the base layer is formed from a cylindrical-phase block copolymer material which, upon annealing, forms lines of half-cylinders in a polymer matrix extending the length and oriented parallel to the sidewalls and floor of the trenches. The assembled base film can then be used as a template for inducing the ordering of an overlying lamellar-phase block copolymer film such that the lamellar domains of the annealed film are oriented perpendicularly and registered to the underlying pattern of the base film within the trenches.
To produce a base polymer film within the trenches using a lamellar-phase block copolymer, the surface of the sidewalls and edges of the trenches are preferential wetting by one block of the copolymer and the trench floors are neutral wetting (equal affinity for both blocks of the copolymer) to allow both blocks of the copolymer material to wet the floor of the trench. Entropic forces drive the wetting of a neutral wetting surface by both blocks, resulting in the formation of a layer of perpendicular lamellae across the width of each trench.
In an embodiment shown in
A neutral wetting surface can be provided, for example, by applying a neutral wetting polymer to form a layer 12 on the surface of the substrate 10. In the use of a self-assembling (SA) diblock copolymer composed of PS-b-PMMA, a random PS:PMMA copolymer brush layer (PS-r-PMMA)) which exhibits non-preferential or neutral wetting toward PS and PMMA can be applied by spin-coating onto the surface of substrate 10. The brush can be affixed by grafting (on an oxide substrate) or by cross-linking (any surface) using UV radiation or thermal processing. For example, a random copolymer solution composed of PS and PMMA with hydroxyl group(s) (e.g., about 58% PS) can be applied to the surface of the substrate 10 as a layer about 5-10 nm thick and grafted by heating at about 160° C. for about 48 hours.
In another embodiment, a surface that is neutral wetting to PS-b-PMMA can 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) onto the surface of the substrate 10 prior to forming the material layer 14. 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 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). 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).
Another neutral wetting surface for PS-b-PMMA can be provided by hydrogen-terminated silicon, which can be prepared by a conventional process, for example, by a fluoride ion etch of a silicon substrate 10 (with native oxide present, about 12-15 Å) for example, by immersion in aqueous solution of hydrogen fluoride (HF) and buffered HF or ammonium fluoride (NH4F), by HF vapor treatment, by exposure to hot H2 vapor, or by a hydrogen plasma treatment (e.g., atomic hydrogen).
Referring now to
The trench sidewalls 22 and ends 24 are preferential wetting by one block of the copolymer to induce formation of lamellae as the blocks self-assemble. The material layer 14 defining the trench surfaces can be an inherently preferential wetting material, or in other embodiments, a layer of a preferential wetting material can be applied onto the surfaces of the trenches.
For example, in the use of poly(styrene-block-methyl methacrylate) (PS-b-PMMA), an oxide (e.g., silicon oxide, SiOx) or a clean silicon surface (with native silicon oxide) exhibits preferential wetting toward the PMMA block to result in the assembly of a thin (e.g., ¼ pitch) interface layer of PMMA and alternating PMMA and PS lamellae (e.g., ½ pitch) within each trench in the use of a lamellar-phase block copolymer material. Other preferential wetting surfaces to PMMA can be provided, for example, by silicon nitride, silicon oxycarbide, polymethylmethacrylate (PMMA) polymer grafted to a sidewall material such as silicon oxide, and resist materials such as methacrylate-based resists. For example, a PMMA that is modified with a moiety containing one or more hydroxyl (—OH) groups (e.g., hydroxyethylmethacrylate) can be applied by spin coating and then heated (e.g., to about 170° C.) to allow the OH groups to end-graft to the oxide sidewalls 22 and ends 24 of the trenches. Non-grafted material can be removed from the neutral wetting layer 12 by rinsing with an appropriate solvent (e.g., toluene). See, for example, Mansky et al., Science, 1997, 275, 1458-1460, and In et al., Langmuir, 2006, 22, 7855-7860, the disclosures of which are incorporated by reference herein.
The trench sidewalls, edges and floors influence the structuring of the array of nanostructures within the trenches. The boundary conditions of the trench sidewalls in both the x- and y-axis impose a structure wherein each trench contains n number of features (i.e., lamellae, cylinders, etc.). Factors in forming a single array or layer of nanostructures within the trenches include the width and depth of the trench, the formulation of the block copolymer to achieve the desired pitch (Lo), and the thickness (t) of the copolymer film.
The trenches 16 are constructed with a width (wt) such that a block copolymer (or blend) will self assemble upon annealing into a single layer of “n” structures spanning the width (wt) of the trench, with each structure (i.e., lamellae, cylinders, etc.) being separated by a value of Lo (from center-to-center). The width (wt) of the trenches is a multiple of the inherent pitch value (Lo) of the polymer being equal to or about nLo(“n*Lo”), typically ranging from about n*10 to about n*100 nm (with n being the number of features or structures). The depth (Dt) of the trenches is a multiple of the Lo value of the block copolymer used for the base layer. The application and annealing of a block copolymer material having an inherent pitch value of Lo in a trench having a width (wt) at or about Lo will result in the formation of a single layer of “n” structures spanning the width and registered to the sidewalls for the length of the trench. In some embodiments, the trench dimension is about 50-500 nm wide (wt) and about 1,000-10,000 μm in length (lt), with a depth (Dt) of about 20-200 nm.
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, proximity X-rays, and electron beam (e-beam) lithography, as known and used in the art. Conventional photolithography can attain (at smallest) about 58 nm features.
Referring now to
The thickness (t1) of the diblock copolymer layer 26 is less than the trench depth (Dt) and at or about the Lo value of the copolymer material such that the film layer will self assemble upon annealing to form a single layer of lamellae across the width (wt) of the trench. A typical thickness (t1) of the copolymer film 26 is about ±20% of the Lo value of the copolymer (e.g., about 10-100 nm) to form alternating polymer-rich lamellar blocks having a width of about Lo (e.g., 25-35 nm) in a matrix of another block within each trench. The thickness of the film 26 can be measured, for example, by ellipsometry techniques. As shown, a thin film 26 of the copolymer material can be deposited onto the spacers 20 of the material layer 14; this film will not self-assemble, as it is not thick enough to form structures.
Although diblock copolymers are used in the illustrative embodiments of this disclosure, other types of block copolymers (i.e., 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). One of the polymer blocks of the block copolymer should be selectively and readily removable in order to fabricate an etch mask or template from the annealed film.
In embodiments in which the base or template layer is formed from a lamellar-forming diblock copolymer, the volume fractions of the two blocks (AB) are generally at a ratio between about 50:50 and 60:40. To achieve an annealed base film in which the lamellae are surface exposed, the Chi value of the polymer blocks (e.g., PS and PMMA) at common annealing temperatures is generally small such that the air interface is equally or non-selectively wetting to both blocks. An example of a lamellae-forming symmetric diblock copolymer is PS-b-PMMA with a weight ratio of about 50:50 (PS:PMMA) and total molecular weight (Mn) of about 51 kg/mol.
In embodiments of the invention, 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, e.g., for lamellae, Lo˜(MW)2/3.
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., 2006, 6(9), 2099-2103, the disclosure of which are incorporated by reference herein, which then reduces the stresses that result from such mismatches.
Referring now to
The constraints provided by the width (wt) of the trenches and the character of the copolymer composition combined with preferential or neutral wetting surfaces within the trenches results, upon annealing, in a single layer of n elements (lamellae) across the width (wt) of the trench. The number “n” or pitches of elements (e.g., lamellar blocks) or half-cylinders within a trench is according to the width (wt) of the trench and the molecular weight (MW) of the block copolymer. As shown in
The resulting morphologies of the annealed base film 28 (i.e., perpendicular orientation of lamellae) can be examined, for example, using atomic force microscopy (AFM), transmission electron microscopy (TEM), scanning electron microscopy (SEM).
The annealed and ordered base film 28 is then treated to crosslink the polymer segments to fix and enhance the strength of the self-assembled polymer blocks 30, 32 within the trench 16 (e.g., to crosslink the PS segments). 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. The material 26 outside the trench (e.g., on spacer 20) can then be removed.
For example, in one embodiment, the trench regions can be selectively exposed through a reticle to crosslink only the self-assembled film 28 within the trench 16, and a wash can then be applied with an appropriate solvent (e.g., toluene), to remove the non-crosslinked portions of the film 28 (e.g., material 26 on the spacer 20) leaving the registered self-assembled base film within the trench and exposing the surface of material layer 14 above/outside the trench (e.g., the spacer 20). In another embodiment, the annealed film 28 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 20), and the exposed portions of the film can be removed, for example by an oxygen (O2) plasma treatment. In other embodiments, the spacers 20 are narrow in width, for example, a width (ws) of one of the copolymer domains (e.g., about Lo) such that the material 26 on the spacers is minimal and no removal is required.
Referring now to
The lamellar-phase block copolymer layer 34a is cast onto the base film 28 within the trench 16 to a thickness (t2) at or about the Lo value of the block copolymer material such that, upon annealing, the copolymer film layer will self-assemble to form a single layer of perpendicular-oriented lamellar domains, each having a width (w2) at or about 0.5 Lo.
As shown in
Referring now to
Referring now to
For example, as illustrated in
In embodiments in which the PS phase domains are removed, the openings (slits) are separated by walls composed of the PMMA domains.
In some embodiments, the resulting film 44 has a corrugated surface that defines a linear pattern of fine, nanometer-scale, parallel slits (openings) 46 about 5-50 nm wide and several microns in length (e.g., about 10-4000 μm), the individual slits separated by walls 48 about 5-50 nm wide, providing an aspect ratio ranging from about 1:2 to about 1:20. For example, removal of the PMMA domains affords a PS mask of sublithographic dimensions, for example, a pitch of about 35 nm (17.5 nm PS domain). A smaller pitch can be dialed in by using lower molecular weight diblock copolymers.
The films can be used, for example, as a lithographic template or etch mask to pattern (arrows ↓↓) the underlying substrate 10, for example, by a non-selective RIE etching process, to delineate a series of channels or grooves 50, shown in phantom in
The films provide linear arrays having long range ordering and registration for a wide field of coverage for templating a substrate. The films are useful as etch masks for producing close pitched nanoscale channel and grooves that are several microns in length, for producing features such as floating gates for NAND flash with nanoscale dimensions. By comparison, photolithography techniques are unable to produce channels much below 60 nm wide without high expense. Resolution can exceed other techniques such as conventional photolithography, while fabrication costs utilizing methods of the disclosure are far less than electron beam (E-beam) or EUV photolithographies which have comparable resolution.
A method according to another embodiment of the invention for forming a thin film that defines a linear array pattern utilizing a base layer formed from a cylindrical-phase block copolymer is illustrated with reference to
Referring to
In using a cylindrical-phase block copolymer, the depth (Dt) of the trench 16′ is less than Lo In some embodiments, the trench dimension is about 50-2000 nm wide (wt) with a depth (Dt) of about 15-25 nm. As shown in
The cylindrical-phase block copolymer can be a diblock or multiblock copolymer, and the copolymer material can be formulated as a binary or ternary blend comprising a homopolymer(s), as previously described. In embodiments in which the base layer is formed using a cylindrical-phase diblock copolymer, the volume fractions of the two blocks (AB) are generally at a ratio between about 60:40 and 80:20. An example of a cylindrical phase diblock copolymer material is PS-b-PMMA (Lo=35 nm) composed of about 70% PS and 30% PMMA (weight ratio of 70:30) with a total molecular weight (Mn) of 67 kg/mol to form about 20 nm diameter half-cylinder PMMA domains in a matrix of PS. To achieve an annealed base film in which the half-cylinders are surface exposed, the Chi value of the polymer blocks (e.g., PS and PMMA) at common annealing temperatures and the difference between interfacial energies of each block and the air is generally small, such that the air interface is equally or non-selectively wetting to both blocks.
Referring now to
The annealed base film 28′ is then be treated to crosslink the polymer segments (e.g., to crosslink the PS matrix 32′). As previously described, the polymers can be structured to inherently crosslink, or one or both of the polymer blocks of the copolymer material can be formulated to contain a crosslinking agent.
As shown in
Subsequent annealing of the copolymer layer 34a′ results in a self-assembled film 36a′ composed of a single layer of perpendicular-oriented lamellar-phase domains 38a′, 40a′ in a striped pattern, which are ordered and registered, respectively, to the polymer domains 30′, 32′ of the cylindrical-phase base layer 28′, as illustrated in
Referring now to
The non-ordered copolymer material 34a′, 34b′ remaining on the spacers 20′ can then be removed resulting in the structure shown in
Selective removal of one of the polymer blocks of the layers 36a-b′ and the base film 28′ can then be performed to produce a thin film 44′ with openings/slits that expose the underlying substrate 10′ and can be used as an etch mask. In the removal of the lamellar domains 38a-b′ and the half-cylinders domains 30′ (e.g., PMMA), the matrix 32′ (e.g., PS) situated underneath the half-cylinders 30′ and over the trench floor 18′ remains as shown by the intermediate structure 43′ in
The film can be used, for example, to pattern (arrows ↓↓) the underlying substrate 10′ to delineate a series of channels or grooves 50′, shown in phantom in
A method according to another embodiment of the invention for forming thin films of a cylindrical-phase self assembling block copolymer that define an array of perpendicularly-oriented cylinders in a polymer matrix is illustrated with reference to
As described with reference to
The trenches are also structured such that the trench floor 18″ is neutral wetting to both blocks of the copolymer material, and the sidewalls 22″ and ends 24″ are preferential wetting by the minority block of the copolymer. Entropic forces drive the wetting of a neutral-wetting surface by both blocks, resulting in a perpendicular orientation of the self-assembled cylinders. In the illustrated example, the material layer 14″ is composed of silicon oxide (SiOx) and the substrate 10″ is composed of silicon. As previously described, a neutral wetting layer 12″ can be provided, for example, by applying a neutral wetting polymer on the surface of the substrate 10″ before forming the material layer 14″, and the trenches 16″ can be etched expose the neutral wetting layer 12″ forming the trench floors 18″. For example, in the use of a PS-b-PMMA diblock copolymer, a random copolymer brush layer (e.g., PS-r-PMMA, PS-r-PMMA-r-BCB, etc.) can be blanket deposited and grafted/crosslinked to the substrate 10″. Another neutral wetting surface for PS-b-PMMA can be provided by hydrogen-terminated silicon, or by PS-r-PMMA (˜60 mol % PS) graft polymerized in situ onto H-terminated silicon.
As previously described, sidewalls 22″ and ends 24″ that are preferential wetting toward the PMMA block of a PS-b-PMMA diblock copolymer can be provided by a material layer 14″ composed of silicon oxide (SiOx), silicon nitride, silicon oxycarbide, a PMMA polymer modified with a moiety containing hydroxyl (—OH) group(s) (e.g., hydroxyethylmethacrylate) grafted to a sidewall material such as silicon oxide, and resist materials such as such as methacrylate based resists. Upon annealing, the PMMA block of the PS-b-PMMA copolymer layer will segregate to the sidewalls and ends of the trench to form a wetting layer (30a″ in
As illustrated in
Referring now to
The annealed cylindrical-phase base film 28″ is then treated to crosslink the polymer segments (e.g., to crosslink the PS matrix 32″). As previously described, the polymers can be structured to inherently crosslink, or one or both of the polymer blocks of the copolymer material can be formulated to contain a crosslinking agent. The polymer material remaining on the spacers 20″ can then be removed as previously described.
As shown in
The annealed film 36a″ is then treated to crosslink the polymer segments (e.g., PS matrix 40a″) and the polymer material on the spacers 20″ removed, as previously described. A second layer 34b″ of the cylindrical-phase block copolymer material can be deposited onto the annealed and crosslinked film 36a″ to a thickness (t2) at or about Lo (
One of the block components can then be selectively removed from the film 42″, leaving either the matrix 48″ to produce a film 44a″ composed of a hexagonal array of cylindrical openings 46″ as in
For example, referring to
In another embodiment illustrated in
In an embodiment of a method to produce a one-dimensional (1-D) array of perpendicularly-oriented cylinders as illustrated in
In embodiments to provide a single row of cylinders within a polymer matrix, a trench 16″ is structured to have a width (wt) that is at or about the Lo value of the block copolymer material, a floor 18′″ that is neutral wetting to both blocks of the copolymer material, and sidewalls 22′″ and ends 24′″ that are preferential wetting by the minority block of the copolymer. In the illustrated example, the material layer 14′″ (e.g., SiOx, SiN, etc.) exposed on the sidewalls 22′″ and ends 24′″ is preferential wetting toward the PMMA block of a PS-b-PMMA diblock copolymer, and the substrate 10′″ (e.g., silicon) bears a neutral wetting layer 12′″ (e.g., a neutral wetting polymer, H-terminated silicon) which is exposed at the trench floors 18′″.
A cylindrical-phase diblock copolymer material 26′″ having an inherent pitch at or about Lo (or blend with homopolymers) can be deposited onto the neutral wetting layer 12′″ on the trench floor 18′″ to a thickness (t1) of less than or about equal to the Lo value of the copolymer material to up to about 1.5×Lo (as shown in
Processing can then be continued to form a cylindrical-phase block copolymer layer 36a′″ on the base film (
Selective removal of one of the block components can then be performed resulting in a film 44a′″ composed of the matrix 48′″ with a 1-D array of cylindrical openings 46′″ as in
For example, referring to
In another embodiment depicted in
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 a film comprising nanoscale microstructures, comprising:
- forming a first film comprising a self-assembling block copolymer within a trench in a substrate, the trench having a neutral wetting floor, sidewalls, a width and a length;
- annealing the first film to form a base layer comprising self-assembled polymer domains registered to the sidewalls and extending the length of the trench;
- crosslinking polymer domains of the base layer;
- forming a second film comprising a self-assembling block copolymer over the crosslinked base layer and over the substrate adjacent the trench, the second film having a thickness over the substrate insufficient for the second film to self-assemble to form ordered structures upon annealing;
- annealing the second film within the trench and on the substrate such that said film within the trench self assembles to form polymer domains registered to corresponding polymer domains of the base layer and said annealed film on the substrate outside the trench comprises non-ordered polymer material; and
- crosslinking polymer domains of the second film.
2. The method of claim 1, further comprising:
- forming a third film comprising a self-assembling block copolymer over the crosslinked second film;
- annealing the third film such that said film self assembles to form polymer domains registered to corresponding polymer domains of the second film; and
- crosslinking polymer domains of the third film.
3. The method of claim 1, wherein the second film comprises perpendicularly-oriented, alternating lamellar domains of first and second polymer blocks registered to the annealed base film.
4. The method of claim 3, wherein the base layer comprises perpendicularly-oriented, alternating lamellar domains of the first and second polymer blocks.
5. A method for fabricating a film comprising nanoscale microstructures, comprising:
- forming a first film comprising a self-assembling block copolymer within a trench in a substrate, the trench having a preferential wetting floor, sidewalls, a width and a length;
- annealing the first film to form a base film comprising lines of parallel-oriented half-cylinder polymer domains registered to the sidewalls and extending the length of the trench;
- crosslinking polymer domains of the base film;
- forming a second film comprising a self-assembling block copolymer over the crosslinked base layer and over the substrate adjacent the trench, the second film having a thickness over the substrate insufficient for the second film to self-assemble to form ordered structures upon annealing;
- annealing the second film within the trench and on the substrate to form polymer domains registered to corresponding polymer domains of the base film within the trench, wherein said annealed second film on the substrate outside the trench comprises non-ordered polymer material; and
- crosslinking polymer domains of the second film.
6. The method of claim 1, wherein the base layer and the second film comprise perpendicularly-oriented cylinders of a first polymer domain extending through a matrix of a second polymer domain to the trench floor.
7. The method of claim 6, wherein the base layer comprises a single row of cylinders with a pitch distance between each cylinder of about Lo.
8. The method of claim 1, wherein the trench has a depth of about nLo where n is 2 or greater, and the first film is formed from a lamellar-phase block copolymer.
9. The method of claim 1, wherein the trench has a depth of less than Lo, and the first film is formed from a cylindrical-phase block copolymer.
10. The method of claim 1, further comprising selectively removing one of the polymer domains to form a plurality of openings exposing the floor of the trench.
11. A method for fabricating a film comprising nanoscale microstructures, comprising:
- forming a first film comprising a self-assembling block copolymer within a trench in a substrate, the trench having a neutral wetting floor, sidewalls, a width and a length;
- annealing the first film to form a base layer comprising self-assembled polymer domains registered to the sidewalls and extending the length of the trench;
- crosslinking polymer domains of the base layer;
- forming a second film comprising a self-assembling block copolymer over the crosslinked base layer and over the substrate adjacent the trench, the second film having a thickness over the substrate insufficient for the second film to self-assemble to form ordered structures upon annealing;
- annealing the second film within the trench and on the substrate such that said film within the trench self assembles to form polymer domains registered to corresponding polymer domains of the base layer and said annealed second film on the substrate outside the trench comprises non-ordered polymer material;
- crosslinking polymer domains of the second film;
- removing non-ordered polymer material on the substrate outside the trench; and
- repeating the steps of forming a self-assembling block copolymer film, annealing the film, crosslinking the film, and removing non-ordered polymer material on the substrate outside the trench to form a multi-layered film comprising self-assembled polymer domains registered to underlying and corresponding polymer domains.
12. A method for fabricating a film comprising nanoscale microstructures, comprising:
- forming a first film within a trench in a substrate, the first film comprising a block copolymer comprising first and second polymer blocks and capable of microphase separating and self-assembling upon annealing, the trench having a neutral wetting floor, sidewalls, a width, and a length;
- annealing the first film to cause a microphase separation of the polymer blocks to form a base layer comprising self-assembled polymer domains registered to the sidewalls and extending the length of the trench;
- crosslinking polymer domains of the base layer;
- forming a second film over the crosslinked base layer and over the substrate adjacent the trench, the second film comprising a block copolymer comprising first and second polymer blocks and capable of microphase separating and self-assembling upon annealing, the second film having a thickness over the substrate insufficient to self-assemble to form ordered structures upon annealing;
- annealing the second film within the trench and on the substrate to cause a microphase separation of the polymer blocks to form self-assembled polymer domains of the first polymer block and the second polymer block registered to the corresponding domains of the base layer within the trench, wherein the annealed second film on the substrate outside the trench comprises non-ordered polymer material; and
- crosslinking polymer domains of the self-assembled second film.
13. A method for fabricating a film comprising nanoscale microstructures, comprising:
- forming a first film comprising a lamellar-phase self-assembling block copolymer within a trench in a substrate, the trench having a neutral wetting floor, sidewalls, a width and a length;
- annealing the first film to form a base layer comprising self-assembled lamellar polymer domains spanning the width and extending the length of the trench in a substantially parallel orientation to the sidewalls;
- crosslinking polymer domains of the base layer;
- forming a second film comprising a self-assembling lamellar-phase block copolymer over the crosslinked base layer and over the substrate adjacent the trench, the second film having a thickness over the substrate insufficient for the second film to self-assemble to form ordered structures upon annealing;
- annealing the second film within the trench and on the substrate such that said film within the trench self-assembles to form lamellar polymer domains registered to corresponding lamellar polymer domains of the crosslinked base layer and said annealed second film on the substrate outside the trench comprises non-ordered polymer material; and
- crosslinking polymer domains of the self-assembled second film.
14. The method of claim 13, wherein the trench sidewalls are preferentially wetting.
15. A method for fabricating a film comprising nanoscale microstructures, comprising:
- forming a first film comprising a cylindrical-phase self-assembling block copolymer within a trench in a substrate, the trench having a width, a length, preferential wetting sidewalls, and a preferential wetting floor;
- annealing the first film to form a base layer comprising lines of self-assembled half-cylinder polymer domains spanning the width, registered to the sidewalls and extending the length of the trench in a substantially parallel orientation to the sidewalls within a matrix of a second polymer domain;
- crosslinking polymer domains of the base layer;
- forming a second film comprising a self-assembling block copolymer over the crosslinked base layer and the substrate adjacent the trench, the second film having a thickness over the substrate insufficient for the second film to self-assemble to form ordered structures upon annealing;
- annealing the second film within the trench and on the substrate such that said second film within the trench self assembles to form polymer domains registered to corresponding polymer domains of the base layer, and said annealed film on the substrate outside the trench comprises non-ordered polymer material; and
- crosslinking polymer domains of the self-assembled second film.
16. The method of claim 15, wherein the second film comprises a lamellar-phase self-assembling block copolymer, and the annealed second film comprises perpendicular-oriented lamellar phase polymer domains.
17. A method for fabricating a film comprising nanoscale microstructures, comprising:
- forming a first film comprising a cylindrical-phase self-assembling block copolymer within a trench in a substrate, the trench having a width, a length, preferential wetting sidewalls and a neutral wetting trench floor;
- annealing the first film to form a base layer comprising perpendicular-oriented cylinders of a first polymer domain within and extending through a matrix of a second polymer domain to the trench floor;
- crosslinking polymer domains of the base layer;
- forming a second film comprising a self-assembling block copolymer over the crosslinked base layer;
- annealing the second film within the trench and on the substrate such that said second film self assembles to form polymer domains registered to corresponding polymer domains of the base layer within the trench and said annealed second film on the substrate outside the trench comprises non-ordered polymer material; and
- crosslinking polymer domains of the self-assembled second film.
18. The method of claim 17, wherein the cylinders extend the length of the trench in a single row.
19. The method of claim 17, wherein the cylinders are in a hexagonal array.
20. A method for fabricating a film comprising nanoscale microstructures, comprising:
- forming a first film comprising a cylindrical-phase block copolymer within a trench in a substrate, the trench having preferential wetting sidewalls, a preferential wetting floor, a width and a length;
- annealing the first film to form a base layer comprising parallel lines of surface-exposed half-cylinder domains of the first polymer block in a matrix of the second polymer block, the half-cylinder domains registered to the sidewalls and extending the length of the trench, wherein a pitch distance between each half-cylinder domain is about Lo;
- crosslinking polymer domains of the base layer;
- forming a second film comprising a lamellar-phase block copolymer over the crosslinked base layer and over the substrate adjacent the trench, the second film having a thickness over the substrate insufficient for the second film to self-assemble to form ordered structures upon annealing;
- annealing the second film within the trench and on the substrate such that said film within the trench self assembles to form a single array of perpendicularly oriented, alternating lamellar domains of the first polymer block and the second polymer block registered to corresponding polymer domains of the base layer, and said film on the substrate outside the trench comprises non-ordered polymer material; and
- crosslinking polymer domains of the self-assembled second film.
21. A method for fabricating a film comprising nanoscale microstructures, comprising:
- forming a first film comprising a cylindrical-phase self-assembling block copolymer within a trench in a substrate, the trench having a width, a length, preferential wetting sidewalls, and a neutral wetting floor;
- annealing the first film to form a base layer comprising self-assembled, perpendicular-oriented cylindrical polymer domains of a first polymer domain within and extending through a matrix of a second polymer domain to the trench floor, said cylinders extending the length of the trench in a single array and a substantially parallel orientation to the sidewalls;
- crosslinking polymer domains of the base layer;
- forming a second film comprising a self-assembling cylindrical-phase block copolymer over the crosslinked base layer and over the substrate adjacent the trench, the second film having a thickness over the substrate insufficient for the second film to self-assemble to form ordered structures upon annealing;
- annealing the second film within the trench and on the substrate such that said film within the trench self-assembles to form cylindrical polymer domains registered to corresponding polymer domains of the crosslinked, annealed base layer and said film on the substrate outside the trench comprises non-ordered polymer material; and
- crosslinking polymer domains of the self-assembled second film.
22. A method of etching a substrate, comprising:
- forming an etch mask, comprising: forming a first film comprising a self-assembling block copolymer within a trench in a substrate, the trench having a neutral wetting floor, sidewalls, a width and a length; annealing the first film to form a base layer comprising self-assembled polymer domains registered to the sidewalls and extending the length of the trench; crosslinking polymer domains of the base layer; forming a second film comprising a self-assembling block copolymer over the crosslinked base layer and over the substrate adjacent the trench, the second film having a thickness over the substrate insufficient for the second film to self-assemble to form ordered structures upon annealing; annealing the second film within the trench and on the substrate such that said film within the trench self assembles to form polymer domains registered to corresponding polymer domains of the base layer and said film on the substrate outside the trench comprises non-ordered polymer material; crosslinking polymer domains of the self-assembled second film; and selectively removing a first polymer domain to form an array of openings separated by a second polymer domain; and
- etching the substrate through the openings of the etch mask.
23. The method of claim 22, wherein the openings have an aspect ratio of about 1:2 to about 1:20.
24. The method of claim 22, wherein the openings have a width of about 5-50 nm.
25. The method of claim 22, wherein the base layer and the second film comprise alternating, perpendicular-oriented lamellae of the first and second polymer domains, and selectively removing the first polymer domain forms a linear array of openings extending the length of the trench and parallel to the sidewalls.
26. A method of etching a substrate, comprising:
- forming an etch mask, comprising: forming a base film within a trench in a substrate, the trench having a preferential wetting floor, sidewalls, a width and a length, the base film comprising lines of parallel-oriented half-cylinders of a first polymer domain in a matrix of a second polymer domain, said half-cylinder lines registered to the sidewalls and extending the length of the trench; crosslinking polymer domains of the base film; forming a second film comprising a lamellar-phase block copolymer over the crosslinked base film and over the substrate adjacent the trench, the second film having a thickness over the substrate insufficient for the second film to self-assemble to form ordered structures upon annealing; annealing the second film within the trench and on the substrate such that said second film within the trench self assembles to form the lamellar domains registered to corresponding polymer domains of the base layer and said second film on the substrate outside the trench comprises non-ordered polymer material; crosslinking polymer domains of the second film; selectively removing lamellar domains of the second film and the underlying half-cylinders of the base layer to form a linear array of openings extending the length of the trench and parallel to the sidewalls; and removing a portion of the matrix to extend said openings to expose the floor of the trench; and
- etching the substrate through the openings of the etch mask.
27. A method of etching a substrate, comprising:
- forming an etch mask, comprising: forming a base film comprising a first block copolymer within a trench in a substrate, the trench having a neutral wetting floor, sidewalls, a width and a length, the base film comprising perpendicular-oriented cylinders of a first polymer domain in a matrix of a second polymer domain, said cylinders extending through the matrix to the trench floor; crosslinking polymer domains of the base film; forming a second block copolymer film over the crosslinked base film and over the substrate adjacent the trench, the second block copolymer film having a thickness over the substrate insufficient for said film to self-assemble to form ordered structures upon annealing; and annealing the second block copolymer film within the trench and on the substrate such that said second block copolymer film within the trench self assembles to form perpendicular-oriented cylinders of a first polymer domain registered to corresponding perpendicular-oriented cylinders of the base layer and said second block copolymer film on the substrate outside the trench comprises non-ordered polymer material; crosslinking polymer domains of the second film; and selectively removing the first polymer domain to form an array of cylindrical openings; and
- etching the substrate through the openings of the etch mask.
28. The method of claim 1, further comprising removing the non-ordered polymer material on the substrate outside the trench.
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Type: Grant
Filed: Apr 20, 2007
Date of Patent: Feb 28, 2012
Patent Publication Number: 20080286659
Assignee: Micron Technology, Inc. (Boise, ID)
Inventor: Dan B. Millward (Boise, ID)
Primary Examiner: Anita Alanko
Attorney: Whyte Hirschboeck Dudek SC
Application Number: 11/738,169
International Classification: H01L 21/302 (20060101); B82Y 40/00 (20110101);