# Patent

## Title
Solvent annealing block copolymers on patterned substrates

## Abstract

Provided herein are block copolymer thin film structures and methods of fabrication. Aspects described herein include methods of directed self-assembly of block copolymers on patterns using solvent annealing, and the resulting thin films, structures, media or other compositions. According to various embodiments, solvent annealing is used direct the assembly of block copolymers on chemical patterns to achieve high degrees of pattern perfection, placement of features at the precision of the lithographic tool used to make the chemical pattern, improved dimensional control of features, improved line edge and line width roughness, and resolution enhancement by factors of two to four or greater.

## Background
CROSS-REFERENCE TO RELATED APPLICATION
This application claims benefit under 35 U.S.C. §119(e) to U.S. Provisional Patent Application No. 61/440,354, filed Feb. 7, 2011, titled “Solvent Annealing Block Copolymers On Patterned Substrates,” which application is incorporated by reference herein in its entirety.


STATEMENT OF GOVERNMENT SUPPORT
This invention was made with government support under 0520527 awarded by the National Science Foundation. The government has certain rights in the invention.


FIELD OF THE INVENTION
The invention relates to methods of nanofabrication techniques. More specifically, the invention relates to forming nanoscale structures with block copolymers.
BACKGROUND OF THE INVENTION
Advanced nanoscale science and engineering have driven the fabrication of two-dimensional and three-dimensional structures with nanometer precision for various applications including electronics, photonics and biological engineering. Traditional patterning methods such as photolithography and electron beam lithography that have emerged from the microelectronics industry are limited in the features that can be formed as critical dimensions decrease and/or in fabrication of three-dimensional structures
SUMMARY
Provided herein are block copolymer thin film structures and methods of fabrication. Aspects described herein include methods of directed self-assembly of block copolymers on patterns using solvent annealing, and the resulting thin films, structures, media or other compositions. According to various embodiments, solvent annealing is used direct the assembly of block copolymers on chemical patterns to achieve high degrees of pattern perfection, placement of features at the precision of the lithographic tool used to make the chemical pattern, improved dimensional control of features, improved line edge and line width roughness, and resolution enhancement by factors of two to four or greater.
One aspect relates to a method including providing a substrate pattern; depositing a block copolymer material on the substrate pattern; and inducing the formation of microphase-separated domains in the block copolymer material by solvent annealing. In some embodiments, the substrate pattern has a pattern period (Ls) between 0.8 and 1.2 times a vitrified microdomain period of the block copolymer material in the solvent (Lv). In some embodiments, Lv differs from the bulk period Lo of the block copolymer material. The substrate pattern can also include at least one feature having an effective pattern period that differs from Ls, for example, a bend, a jog, or isolated spot. In some embodiments, the method can further include evaporating the solvent. Examples of solvents include methanol, acetone, carbon disulfide, dimethylformamide, toluene, and tetrahydrofuran. According to various embodiments, all or only a subset of the polymer blocks of the block copolymer material are soluble in the solvent.
The microphase-separated domains can be registered with the substrate pattern after solvent annealing. In some embodiments, they are oriented substantially perpendicular to the substrate. Also in some embodiments, the microphase-separated domains can extend through the entire thickness of the block copolymer material. In some embodiments Ls is between 0.9 Lv and 1.1Lv.
In some embodiments, the interaction parameter (χ) of a block copolymer in the block copolymer material is larger than that of PS-b-PMMA at an equivalent temperature of assembly. Solvent annealing can be performed at temperatures lower than thermal annealing. In some embodiments, solvent annealing is performed at room temperature.
Another aspect relates to method including providing a block copolymer film on a substrate pattern and exposing the block copolymer film on the substrate pattern to a solvent to thereby direct the assembly of the block copolymer film. The method can further include evaporating the solvent. The solvent can be evaporated after the assembly of the block copolymer film. In some embodiments, the assembled block copolymer film has smaller features than the bulk block copolymer. In some embodiments, the density of features in the assembled block copolymer film is greater than the substrate pattern density.
Another aspect relates to thin film compositions and nanoscale structures formed using the methods described herein. These and other aspects are described more fully below with reference to the drawings.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows an example of ideal phase behavior of diblock copolymers.
FIGS. 2A and 2B show examples of directed assembly of lamellar and cylindrical ordered domains.
FIG. 3 shows an example of a process flow for fabricating block copolymer (BCP) thin film structures.
FIG. 4 shows top-down SEM images of PS-b-PMMA (95k-b-92k) ultrathin films on unpatterned surfaces (left column) and chemical patterns with a pattern period (Ls) of 70 nm (right column). The films were annealed in acetone vapor for 1.5-46h.
FIG. 5 is a schematic example of a pattern including a varying effective pattern period.
FIG. 6A shows examples of patterns that may be used integrated circuit and logic device fabrication.
FIG. 6B shows examples of types of pattern features that may be used integrated circuit and logic device fabrication.
FIG. 7 shows top-down SEM images of solvent annealing induced directed assembly on 1:1 chemical patterns. 30 nm thick PS-b-P2VP (40k-b-40k) films were annealed in acetone vapor on chemical patterns with periods of Ls=40 nm, 42.5 nm, 45 nm, 47.5 nm, 50 nm, 52.5 nm, 55 nm, and 57.5 nm.
FIG. 8 shows top-down SEM images of PS-b-PMMA (95k-b-92k) ultrathin films annealed in acetone vapor for 10 h on chemical patterns with Ls=75 nm and bend angles of θ=60°, 90°, 120°, and 150°.
FIG. 9 shows top down SEM images of solvent annealing induced directed assembly on 1:2 chemical patterns. 30 nm thick PS-b-P2VP (40k-b-40k) films were annealed in acetone vapor on chemical patterns with periods of Ls=80 nm, 90 nm, 100 nm, and 110 nm.
FIG. 10 shows top down SEM images of solvent annealing induced triple and quadruple density multiplication on chemical patterns. 30 nm thick PS-b-P2VP (40k-b-40k) films were annealed in acetone vapor on chemical patterns with periods of Ls=138 nm and 184 nm.
FIGS. 11A and 11B show images of acetone annealed PS-b-P2VP (40k-b-40k) films on PS60.8%-r-P2VP-r-PHEMA2% grafted silicon substrates. FIG. 11A shows a top down SEM image. FIG. 11B shows a cross-sectional SEM image of a 200 nm thick film.
FIG. 12 shows a schematic illustration of operations in processes of directing assembly of BCPs on 1:1 and 1:2 chemical patterns via solvent annealing.
FIG. 13 shows a schematic illustration of an experimental setup for solvent annealing of BCP thin films.
FIG. 14 shows solvent annealing induced directed assembly of relatively thick PS-b-P2VP (40k-b-40k) films on 1:1 chemical patterns with Ls=42.5 nm, 45 nm, 47.5 nm, and 50 nm. Top down images of assembled films of thickness 140 nm and 235 nm are shown.
FIG. 15 shows top-down SEM images of PS-b-PMMA (95k-b-92k) films on substrates grafted by PS—OH, PS57%-r-PMMA-OH, and PMMA-OH. The films were annealed in acetone vapor for 1.5 h, 5 h, and 44 h.
FIG. 16 shows top-down SEM images of PS-b-PMMA (95k-b-92k) films annealed in acetone vapor for 5h on chemical patterns with Ls=70 nm, 80 nm, and 90 nm.
FIG. 17 shows top-down SEM images of PS-b-PMMA (95k-b-92k) films annealed in acetone vapor for 10 h on chemical patterns with Ls=60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, and 95 nm.
FIG. 18 shows top-down SEM images of the epitaxial assembly of PS-b-PMMA (95k-b-92k) films on grating chemical patterns with Ls=60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, and 90 nm after exposure to acetone vapor for 46 h.
FIG. 19 is a process flow diagram illustrating operations in creating and using a BCP thin film composition.



DETAILED DESCRIPTION
Reference will now be made in detail to specific embodiments of the invention. Examples of the specific embodiments are illustrated in the accompanying drawings. While the invention will be described in conjunction with these specific embodiments, it will be understood that it is not intended to limit the invention to such specific embodiments. On the contrary, it is intended to cover alternatives, modifications, and equivalents as may be included within the spirit and scope of the invention. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be practiced without some or all of these specific details. In other instances, well known process operations have not been described in detail in order not to unnecessarily obscure the present invention.
Provided herein are methods of directed self-assembly of block copolymers on patterns using solvent annealing, and the resulting thin films, structures, media or other compositions. Self-assembling materials spontaneously form structures at length scales of interest in nanotechnology. Block copolymers (also referred to herein as BCPs) are a class of polymers that have two or more polymeric blocks. The structure of diblock copolymer AB, also denoted A-b-B, may correspond, for example, to AAAAAAA-BBBBBBBB. FIG. 1 shows theoretical phase behavior of an A-b-B diblock copolymer. The graph in FIG. 1 shows, χN (where χ is the Flory-Huggins interaction parameter and N is the degree of polymerization) as a function of the volume fraction, f, of a block (A) in a diblock (A-b-B) copolymer. χN is related to the energy of mixing the blocks in a diblock copolymer and is inversely proportional to temperature. FIG. 1 shows that at a particular temperature and volume fraction of A, the diblock copolymers microphase separate into domains of different morphological features (also referred to as microdomains). As indicated in FIG. 1, when the volume fraction of either block is around 0.1, the block copolymer will microphase separate into spherical domains (S), where one block of the copolymer surrounds spheres of the other block. As the volume fraction of either block nears around 0.2-0.3, the blocks separate to form a hexagonal array of cylinders (C), where one block of the copolymer surrounds cylinders of the other block. And when the volume fractions of the blocks are approximately equal, lamellar domains (L) or alternating stripes of the blocks are formed. Representations of the cylindrical and lamellar domains at a molecular level are also shown. Domain size typically ranges from 2 nm or 3 nm to 50 nm. The phase behavior of block copolymers containing more than two types of blocks (e.g., A-b-B-b-C), also results in microphase separation into different domains. The size and shape of the domains in the bulk depend on the overall degree of polymerization N, the repeat unit length a, the volume fraction f of one of the components f, and the Flory-Huggins interaction parameter, χ.
A block copolymer material may be characterized by bulk lattice constant or period L0. For example, a lamellar block copolymer film has a bulk lamellar period or repeat unit, L0 equal to the width of two stripes. For cylindrical and spherical domain structures, the periodicity L0 of the bulk domain structures can be characterized by a center-to-center distance between the cylinders or spheres, e.g., in a hexagonal array. While the FIG. 1 shows an example of phase behavior of a diblock copolymer for illustrative purposes, the phase behavior of triblock and higher order block copolymers also can results in microphase separation into different architectures.
FIGS. 2A and 2B show examples of directed assembly of lamellar (FIG. 2A) and cylindrical (FIG. 2B) ordered domains. Patterning of layers 205a and 205b is indicated at 210a and 210b, respectively, with the arrows representing radiation appropriate to pattern a layer, such as x-ray radiation, extreme ultraviolet (EUV) radiation or electron beam radiation. Layers 205a and 205b, which can be referred to as patternable layers or imaging layers, are layers of material that can be selectively altered to create a chemical pattern. In one example, a layer of polystyrene (PS) brushes anchored to a surface is used as an imaging layer. FIG. 2A shows layer 205a on a substrate 203, which can be a silicon (Si) wafer or other appropriate substrate. Patterning can include use of a resist as generally known to one having ordinary skill in the art to expose regions of the patternable layer to form the desired pattern, followed by chemical modification of the exposed regions; for example, exposed regions of a PS brush layer can be oxidized. Chemically patterned surfaces 207a and 207b are indicated at 220a and 220b, respectively, with surface 207a patterned with alternating stripes and surface 207b patterned with an array of spots. Block copolymer material 209a and 209b is deposited on the chemically patterned surfaces 207a and 207b, respectively, as indicated at 230a and 230b. The block copolymer material 209a and 209b is then induced to undergo microphase separation.
The chemically patterned surfaces 207a and 207b can direct the assembly of the block copolymer material 209a and 209b such that the phase-separated domains are oriented perpendicular to the underlying surface and registered with the chemical pattern. The assembled phase-separated thin films 211a and 211b are shown at 240a and 240b, respectively. Thin film 211a includes lamellae of first polymer 213a and second polymer 215a aligned with the stripes of the underlying chemical pattern. Thin film 211b includes cylinders of a first polymer 213b in a matrix of a second polymer 215b, with the cylinders and matrix aligned with the underlying chemical pattern.
Periodic patterns formed on substrates or in thin block copolymer films may also be characterized by characteristic lengths or spacings in a pattern. Ls is used herein to denote the period, pitch, lattice constant, spacing or other characteristic length of a pattern such as surface pattern. For example, a lamellar period Ls of a two-phase lamellar pattern may be the width of two stripes. In another example, a period Ls of an array of spots may be the center-to-center distance of spots.
Surface energy, as used herein, refers to energy at the surface between a condensed and non-condensed phase, such as a solid block copolymer thin film or block copolymer film in the melt and a gas or vacuum. Interfacial energy, as used herein, refers to energy at the surface between two condensed phases, such as a solid block copolymer thin film or block copolymer thin film in the melt and a liquid or solid.
In embodiments described herein, microphase separation of the BCP thin films is induced by solvent annealing. According to various embodiments, solvent annealing can be used direct the assembly of BCPs on prepatterns, including chemical prepatterns, to achieve desirable attributes of directed assembly processes, including high degrees of pattern perfection, placement of features at the precision of the lithographic tool used to make the chemical pattern, improved dimensional control of features, improved line edge and line width roughness, and resolution enhancement by factors of two to four or greater. In addition, the methods described herein can achieve the canonical set of feature geometries used in the fabrication of integrated circuits. Solvent annealing may be advantageously used to direct self-assembly of BCPs that contain blocks with dissimilar surface energies, are thermally instable, or cannot reach thermal equilibration due to mass transport or other limitations. For example, large-molecular-weight BCPs have extremely slow chain mobility and demands high annealing temperature that may exceeds their thermal degradation temperature. Solvent annealing also provides additional control on BCP morphologies and periods.
FIG. 3 is an example of a process flow for fabricating BCP thin film structures. First, a patterned substrate is provided at block 301. The substrate can be patterned with regions of different chemical compositions. Schematic examples of patterned substrates are shown at 220a and 220b in FIGS. 2A and 2B, discussed above. The substrate pattern will direct the assembly of the BCP thin film and so corresponds to the desired morphology of the thin film. In some embodiments, the substrate pattern period Ls is commensurate to the vitrified BCP microdomain period Lv of the BCP material to be deposited on the pattern.
The BCP material is then spun on (or otherwise deposited) on the patterned substrate at block 303. Schematic examples of unassembled BCP material on patterned substrates are shown at 230a and 230b in FIGS. 2A and 2B. The process continues at block 305 with directing the assembly of the BCP film in the presence of a solvent. In some embodiments, the substrate pattern is replicated in the assembled BCP film as described above. The absorbed solvent effectively lowers the glass transition temperature Tg, and can increase BCP chain mobility to obtain mass transport that may be unobtainable thermal annealed systems. Directed assembly of the BCP films can be performed at lower temperatures than “pure” BCPs, i.e., BCPs without absorbed solvent. Further, in some embodiments, the assembled BCP thin films have smaller periods than obtainable with pure BCPs.
Once the BCP film has been directed to assemble to the desired morphology, the solvent is allowed to evaporate at block 307. In some embodiments, block 307 can involve reducing the thickness of the BCP film while the lateral dimensions of the microdomains remain stable. That is, the microdomains may shrink in the z-direction orthogonal to the plane of the substrate, keeping their dimensions in the x- and y-directions. It is noted that in some embodiments, solvent evaporation does not contribute to the assembly of the BCP films in the process described with reference to FIG. 3. Without being bound by a particular theory, it is believed that the BCP films achieve a stable or meta-stable equilibrium state in block 305.
According to various embodiments, the solvent can be selective or non-selective. A selective solvent is one that prefers one of the blocks of the BCP. In the case of a triblock or higher order BCP, a selective solvent may prefer two or more blocks over another block of the BCP. A non-selective or neutral solvent is a solvent in which all blocks of the BCP have good solubility.
The choice of solvent can affect the maximum solvent volume fraction, morphology, and domain size of the assembled film. Phases of BCP/solvent systems can depend on the volume fraction of the solvent as well as the temperature and relative volume fractions of the blocks. For example, the morphology of a symmetric diblock copolymer annealed in a selective solvent at low temperature may change from lamellae, gyroid, cylinder, sphere, and micelles upon increase of solvent fraction.
Table 1, for example, below shows the effect of solvent choice on the swelling ratio, maximum volume fraction and morphology of a lamella-forming symmetric polystyrene-block-poly(2-vinyl pyridine) (PS-b-P2VP) (40k-b-40.5k) having an L0 of about 53 nm.







TABLE 1







Effect of Solvent Choice on symmetric PS-b-P2VP













Solvent





Swelling Ratio
Volume


Solvent
(max)
Fraction (max)
Morphology
Lv





Methanol
168%
0.63
disordered
n/a


Toluene
115%
0.53
cylindrical
57 nm


DMF
110%
0.52
cylindrical
53 nm


CS2
93.5% 
0.48
cylindrical
63 nm


Acetone
41.2% 
0.30
lamellar
46 nm









Thin films of the PS-2-P2VP on unpatterned surfaces were exposed to the solvent vapor at room temperature for a time period long enough to reach fully swollen state. Swelling ratio is the ratio of the solvent-containing film thickness to the pure film thickness, with the solvent volume fraction determined from the swelling ratio. The solvent volume fraction of a particular BCP at a particular temperature determines the morphology of the BCP. Depending on the nature of the solvent molecules, the swelling ratio of each block and the relative volume fraction may be greatly different, which may lead to different morphologies. While the PS-b-P2VP (40k-b-40k) is lamella forming in the bulk, annealing in methanol resulted in micellar structures, and annealing in toluene, dimethylformamide (DMF) and carbon disulfide (CS2) resulted in parallel cylinders. After being annealed in acetone vapor, PS-b-P2VP (40k-b-40k) showed lamellar morphology, however, with the period Lv decreased by 13% in comparison to L0.
The selectivity of a solvent can vary according to the desired embodiment. Table 2 shows solvent selectivity for blocks of a PS-b-PMMA diblock for toluene, acetone and CS2.







TABLE 2







Solubility of PS-b-PMMA blocks











Solvent
PS
PMMA







Toluene
Soluble
Soluble




(χPS-Toluene = 0.34)
(χPMMA-Toluene = 0.45)



CS2
Soluble
Insoluble




(χPS-CS2 = 0.01)
(χPMMA-CS2 = 1.2)



Acetone
Insoluble
Soluble




(χPS-Acetone = 1.1)
(χPMMA-Acetone = 0.29)










A neutral or non-selective solvent is a good solvent for both blocks of a diblock copolymer, and can decrease the effective interaction parameter such that χeff=χ(1−fsol) where f is the volume fraction of the solvent. A strong selective solvent can increase the degree of segregation relative to the melt state. Accordingly, in some embodiments, domain size can be controlled by appropriately selecting a solvent.
Solvent annealing of symmetric PS-b-PMMA ultra-thin films led to different morphologies according to the varying solvent selectivity. A good solvent for both blocks, tetrahydrofuran (THF) induced a terraced morphology. Annealing in CS2, a PS-selective solvent, caused disordered micellar structure. While annealed in acetone, a PMMA-selective solvent, the thin films exhibited different morphologies by varying the solvent annealing time.
FIG. 4 shows top-down SEM images of PS-b-PMMA (95k-b-92k) ultrathin films on non-patterned area (left column) and alternating stripe chemical patterns with Ls=70 nm (right column). The films were annealed in acetone vapor for 1.5-46 h.
On the non-patterned area (PS—OH grafted silicon substrate), the BCP film morphology changes along with increasing exposure time to acetone vapor. The film became featureless after 1.5 h annealing (not shown). Dots of PMMA started to appear and dominate the whole film after 5 h annealing. 10 h exposure to acetone vapor resulted in fingerprint patterns. These stripped structures turned into and were maintained in honeycomb structure (PS spheres) with increasing annealing time. The periodicity Lv of the PMMA dots, stripes, and PS spheres are all approximately 75 nm (rod-to-rod distance for PMMA dots and PS spheres). All three different BCP morphologies were directed to assemble by the grating chemical patterns. With different annealing times, the BCP films appeared the same morphologies on the Ls=70 nm chemical patterns as those on the non-patterned areas. PMMA dots aligned on the chemical patterns emerged after 3 h annealing (not shown) and formed pseudo long-ranged ordered hexagonal dot patterns after 5 h annealing. Long-range ordered and well registered stripes were observed after 10 h annealing. Annealing for longer time (15 h) resulted in the mixture of aligned stripes and PS spheres. Close packed honey-comb shape PS spheres formed on chemical patterns after annealing for 46 h.
The results in FIG. 4 demonstrate that morphology can be controlled by anneal time as well as by choice of solvent. The results also demonstrate that any type of feature formed in the bulk or on an unpatterned surface can be directed to assemble by the appropriate chemical pattern.
In some embodiments, the solvent also may be selected to manipulate the difference between blocks of the block copolymer in surface energy at the free surface. For example, in certain embodiments, a solvent that reduces the difference in surface energy between block A and the free surface and block B and the free surface. This can facilitate microdomains that are perpendicular to the substrate extending through the entire thickness of the thin film. In some embodiments, a non-preferential or weakly preferential solvent may be chosen to reduce the difference.
Thermal annealing can result in a thin top layer of one block due to different surface energies at the free surface. For example, thermal annealing of PS-b-P2VP can result in PS on the PS-b-P2VP films due to the smaller surface tension of PS. An additional etching may remove the top layer, which may alter the surface properties and cause the decrease of the pattern aspect ratio. In some embodiments, the solvent may mediate the polymer-air (or other free surface) interface energy such that no top wetting layer forms, with the microdomains extending through the thickness of the BCP film.
In some embodiments, a BCP having blocks with a higher differential surface energy than PS-b-PMMA at the temperature of assembly may be used, facilitated by the solvent. Due to the very similar surface tension (γs) between the PS and PMMA blocks at about 170-230° C., PS-b-PMMA facilitates generating perpendicularly oriented microdomains (e.g., lamellae or cylinder) through a film thickness. BCPs that have smaller dimensions, higher etching selectivity or other specific properties than PS-b-PMMA generally contain blocks with dissimilar γs, which can cause preferential wetting of one block at the free surface of the film and/or lead to parallel microdomain structures. The methods described herein can allow the formation of perpendicular domains of these BCPs through the thickness of the film. The pattern formed by the perpendicular structures can be readily transferred after removal of one domain by wet or dry etching.
One factor in achieving perfect or near perfect assembly on chemical patterns is the selective interaction between BCP blocks and the chemically patterned surface. During solvent annealing, the solvent to surface interaction may screen the interaction between BCP blocks and chemical patterns. The screening effect may increase with dilution of the BCP films. In some embodiments, the methods may include controlling solvent volume fraction and the solvent selectivity. For example, both high selectivity and low solvent volume fraction may be used such that the interaction between at least one block and a patterned region (e.g., a PS block and PS brush patterned features) is sufficient to induce directed self-assembly. Relatively low solvent volume fractions, e.g., less than about 50% or less than about 40%, can facilitate directed assembly in some embodiments, though for some systems a higher solvent volume fraction may be tolerated.
In some embodiments, solvent annealing conditions, including solvent, temperature, and solvent volume fraction are selected such that the microdomain structures are formed in the solvated state, rather than during solvent evaporation. Without being bound by a particular theory, it is believed that directed assembly on chemical patterns via solvent annealing follows a mechanism in which the quasi-equilibrium is achieved the solvated state and quenched, rather than a nucleation and growth mechanism by which ordering forms during solvent evaporation at the interface with free surface and propagates down. In some embodiments, however, there may be some amount of ordering induced by nucleation at the free surface interface, in addition to forming microdomain structures in the solvated state.
In some embodiments, the solvent annealing conditions are chosen such that equilibrium or quasi-equilibrium ordered structures are formed in the solvated state and are retained after solvent evaporation. In some embodiments, the solvent annealing conditions are further chosen such the domains are ordered perpendicular to the substrate. The films are annealed for a sufficient time to reach an equilibrant state and can achieve perfect or nearly perfect assembly on chemical patterns. Without being bound by a particular theory, it is believed that after a BCP film is exposed to solvent vapor, the chain mobility increases with swelling ratio and when the chain mobility is sufficient, microdomain structures forms. The morphology depends on the solvent and the swelling ratio, and does not change over time at the same swelling ratio. For instance, parallel hexagonally packed cylinders and stretched body centered cubic (BCC) packed spheres can be formed while annealing PαMS-b-PHOST thin films in THF and acetone respectively. In the rapidly dried films, both morphologies are maintained except with compression in the direction normal to the substrates due to the uniaxial contraction.
The pattern used to direct the assembly of the BCP can be regular, such as an alternating stripe pattern, a hexagonal array of spots, etc., or contain irregular features such as bends, jogs and T-junctions, as well or other irregular features in which the effective pattern period is non-constant. An example is depicted in FIG. 5, which shows the distance between interfaces of an irregular feature (a bend) in a pattern. With Ls equal to the width of two stripes, assuming a symmetric pattern where the shaded and unshaded stripes are of equal width, the distance between interfaces is 1⁄2Ls along the unbent linear portions of the pattern. At the bend corner, however, the distance between interfaces is Ls/2sin(θ/2)—comparable to having a period of Ls/sin(θ/2). Thus the effective period at the bend corner Lc is Ls/sin(θ/2). The bent nonlinear portions of the pattern in FIG. 5 have different periods than the linear portions. FIG. 6B depicts other features that may be included in a pattern in certain embodiments, including bend, t-junction and jog features that have non-constant effective pattern periods. Patterns of spots and parallel or non-parallel lines may also have varying spacing and periods across a pattern. In some embodiments, such patterns can be used for pattern transfer and integrated circuit fabrication. For example, FIG. 6A shows generalized layouts for gate layers for a NAND2 or NOR2 layout and an inverter layout. The NAND2 or NOR2 gate layer includes a jog and the inverter gate layer includes both a t-junction and sharp 90° angles. In addition to lamellae-forming BCPs, in some embodiments, cylinder-forming or sphere-forming BCPs can be directed to assemble on spot chemical patterns, which may find applications in bit patterned storage media. Many integrated circuit layouts can be for pattern transfer or fabrication of contacts or contact holes. These features may be patterned either as dense arrays or as isolated structures, for example with sub-32 nm, sub-22 nm or smaller critical dimensions.
The pattern period, or range of effective pattern periods, is commensurate with the vitrified BCP microdomain period, Lv. The vitrified BCP microdomain period Lv is the period of the solvated block copolymer when the BCP has reached an immovable state, and is dependent on the particular solvent used. The Lv of an assembled BCP can be measured experimentally before or after solvent evaporation by X-ray scattering or other appropriate measurement, or can be obtained through simulation or reference. While the slow dynamics of many BCP systems indicate that the lateral dimensions of the ordered BCP films do not change upon fast evaporation, it is possible that there may be some small (e.g., on the order of a 1 or 2 nm) amount of change in the measured period. In some embodiments, a desired pattern period or range of pattern periods in an assembled film is identified, with the BCP/solvent system having a commensurate Lv then chosen.
It is noted that the Lv may be significantly different that the natural period Lo of the block copolymer. In some embodiments, the range of effective pattern periods is between +/−0.1Lv, though depending on the particular system a wider range of pattern periods may be tolerated, e.g., +/−0.2Lv, to direct the assembly of the BCP. For example, triblock or higher order BCPs may tolerate a 20% or higher discrepancy between the pattern period and Lv. The chemical pattern matches the swollen domain sizes such that solvent-swollen block copolymer material can equilibrate in the presence of the chemical pattern.
FIG. 7 shows SEM images of 30 nm thick PS-b-P2VP (40k-b-40k) films cast on chemical patterns of 40 nm≦Ls≦57.5 nm and annealed in acetone vapor. The vitrified BCP microdomain period Lv is about 46 nm (see Table 1). The registration and ordering of the BCP microdomains is nearly perfect over the entire imaged area for Ls=42.5, 45, 47.5 and 50 nm, with only a few dislocation defects observed on the Ls 40 and 52.5 nm prepatterns. The period of these ordered and registered BCP domains (Lp) equals Ls. This shows that for this BCP/solvent system, a pattern having a period or range of effective periods of +/−0.15Lv may be replicated. When Ls=55 and 57.5 nm, the BCP film was largely disordered and unregistered with respect to the prepatterns, however a small portion of lamellae were oriented in the direction of the prepattern at Ls=55 nm.
In some embodiments, patterns having one or more irregular features that have effective periods that differ significantly from Lv can direct assembly of the BCP. FIG. 8 shows the top-down SEM images of PS-b-PMMA (95k-b-92k) films directed to assembly via solvent annealing on irregular patterns. The BCP films were annealed in acetone for 10 h. Directed assembly with high perfection was observed on the linear portions of the chemical patterns. On bended chemical patterns, the corner-to-corner period, Lc, increases with bend angle, θ (see inset in the θ=90° image, which shows the angle 180°−θ). The corner-to-corner period, Lc=Ls/cos(θ/2) is 86.6 nm, 106.1 nm, 150 nm, and 289.8 nm for 60°, 90°, 120°, and 150° bends respectively. Defects at the corner would be expected Lc is larger than the largest Ls of chemical patterns that can direct nearly perfect assembly. For PS-b-PMMA (95k-b-92k) annealed in acetone for 10 h, Lv is about 75 nm, with the largest chemical pattern period that directed near perfect assembly was about 85 nm. Using solvent annealing, directed assembly was even observed on chemical patterns with 60°, 90° and 120° bends, despite having an effective pattern period ranging from 1.15 Lv to about 2Lv. Without being bound by a particular theory, it is believed that the absorbed solvent redistributes to accommodate irregular features and facilitate defect-free assembly at bends and other irregular features.
In some embodiments, directed assembly via solvent annealing can involve density multiplication of the substrate pattern. Density multiplication refers the density of features in an assembled film being greater than that of the patterned substrate. The substrate pattern can have a period Ls commensurate with nLv with n equal to an integer greater than 1. For example, Ls may be nLv+/−0.1nLv. FIG. 9 shows top-down SEM images of assembled PS-b-P2VP (40k-b-40k) on a series of chemical patterns with 80 nm≦Ls≦110 nm or about 1.75Lv≦Ls≦2.4Lv. Assembly with high perfection occurred on chemical patterns with Ls=90 nm (about 1.95Lv) and 100 nm (about 2.2Lv) except a few dislocation defects were observed on Ls=100 nm prepatterns. At Ls=80 nm and 110 nm there are more dislocation defects and unregistered lamellae. FIG. 10 shows top-down SEM images of thin films of PS-b-P2VP (40k-b-40k) directed to assemble on chemical patterns with Ls of 138 nm (about 3Lv) and 184 (about 4Lv).
Parameters
The following are examples of substrates, patterning techniques, patterns, and block copolymer materials that may be used in accordance with certain embodiments.
Substrate
Any type of substrate may be used. In semiconductor applications, wherein the block copolymer film is to be used as a resist mask for further processing, substrates such as silicon or gallium arsenide may be used. For patterned media applications, a master pattern for patterned media may be made on almost any substrate material, e.g., silicon, quartz, or glass.
According to various embodiments, the substrate may be provided with a thin film or imaging layer thereon. The imaging layer may be made of any type of material that can be patterned or selectively activated. In a certain embodiment, the imaging layer comprises a polymer brush or a self-assembled monolayer. Examples of self-assembled monolayers include self-assembled monolayers of silane or siloxane compounds, such as self-assembled monolayer of octadecyltrichlorosilane.
In certain embodiments, the imaging layer or thin film to be patterned is a polymer brush layer. In certain embodiments, the polymer brush may include one or more homopolymers or copolymers of the monomers that make up the block copolymer material. For example, a polymer brush of at least one of styrene and methyl methylacrylate may be used where the block copolymer material is PS-b-PMMA. One example of a polymer brush to be used in a thin film is PSOH. In some embodiments, a pattern may be provided without an underlying substrate, for example as an unsupported polymer film.
Patterning
Patterns may be formed by any method, including all chemical, topographical, optical, electrical, mechanical patterning and all other methods of selectively activating a substrate. A chemically patterned surface can include, for example, patterned polymer brushes or mats, including copolymers, mixtures of different copolymers, homopolymers, mixtures of different homopolmyers, block oligomers, and mixtures of different block oligomers. In embodiments where a substrate is provided with an imaging layer (such as a self-assembled monolayer or polymer brush layer) patterning the substrate may include patterning the imaging layer. In some embodiments, patterning may include forming background regions that are non-preferential or weakly preferential to the component blocks of the BCP.
A substrate may be patterned by selectively applying the pattern material to the substrate. In some embodiments, a resist can be patterned using an appropriate method. The substrate patterning may include top-down patterning (e.g. lithography), bottom-up assembly (e.g. block copolymer self-assembly), or a combination of top-down and bottom-up techniques. In certain embodiments, the substrate is patterned with x-ray lithography, extreme ultraviolet (EUV) lithography or electron beam lithography. In certain embodiments, a chemically patterned surface can be prepared using a molecular transfer printing method as disclosed in US 2009-0260750, titled “Molecular Transfer Printing Using Block Copolymers,” incorporated by reference herein.
Pattern
Substrate surface patterns, or other patterns that direct the assembly of block copolymer (as well as the block copolymer material used) affect self-assembled domains that result from the processes described above. The surface pattern and the BCP film deposited on it can be chosen to achieve the desired pattern in the block copolymer film. In certain embodiments, there is a 1:1 correspondence between the number of features patterned on the substrate (by e-beam lithography or other technique) and the number of features in the self-assembled block copolymer film. In other embodiments, there may be a 1:2, 1:4 or other correspondence, with the density of the substrate pattern multiplied as described in US 2009-0196488, titled “Density Multiplication And Improved Lithography By Directed Block Copolymer Assembly” incorporated by reference herein. It should be noted that in certain cases, the 1:1 correspondence (or 1:2, etc.) might not be exactly 1:1 but about 1:1, e.g., due to imperfections in the substrate pattern.
The directed assembly may or may not be epitaxial according to various embodiments. That is, in certain embodiments, the features as defined by the block copolymer domains in the block copolymer film are located directly above the features in the chemical contrast pattern on the substrate. In other embodiments, however, the growth of the block copolymer film is not epitaxial. In these cases, the chemical contrast (or other substrate pattern) may be offset from the self-assembled domains. Even in these cases, the block copolymer domains are typically spatially registered with the underlying chemical pattern, such that the location of a block copolymer domain in relation to a location of a patterned feature is precisely determined. In some embodiments, registered block copolymer domains are aligned such that an interface between domains overlies an interface between the adjacent pattern features. In some other embodiments, registered domains may be offset from and/or differently sized than the underlying pattern features.
In certain embodiments, the pattern corresponds to the geometry of the bulk copolymer material. For example, hexagonal arrays of cylinders are observed bulk morphologies of certain block copolymers, and a pattern can include a hexagonal array. However, in other embodiments, the substrate pattern and the bulk copolymer material do not share the same geometry. For example, a block copolymer film having domains of square arrays of cylinders may be assembled using a material that displays hexagonal arrays of cylinders in the bulk.
The individual features patterned on the substrate may be smaller than or larger than the mean feature size of the block copolymer domains (or the desired feature size). In certain embodiments, the pattern has at least one dimension within an order of magnitude of a dimension of one domain in the block copolymer material.
In some embodiments, a pattern may include a varying effective pattern period. In some embodiments, a pattern may be characterized as having a pattern period Ls that represents that length scale of uniformly spaced features that may dominate or be a major part of a pattern. For example, the pattern period Ls in the example depicted in FIG. 5 is the width of straight portions of adjacent stripes. Irregular features such as bends and t-junctions may give rise to effective pattern periods that differ from the pattern period Ls. In some embodiments, a pattern may not have any one length scale that dominates the pattern, but have a collection of features and associated effective pattern periods. In some embodiments, the effective pattern period Ls-eff may vary by up to about 30%, 40%, 50% or 100% or greater across the pattern.
Further examples of patterns are described in US-2006-0134556, titled “Methods And Compositions For Forming Aperiodic Patterned Copolymer Films” and in US-2008-0299353, titled “Methods And Compositions For Forming Patterns With Isolated Or Discrete Features Using Block Copolymer Materials,” both of which are incorporated by reference herein.
Solvent/BCP System
Any type of copolymer that undergoes microphase separation in the presence of a solvent may be used. This includes block copolymers that have as components glassy polymers such as PS and PMMA, which have relatively high glass transition temperatures, as well as more block copolymers that have more elastomeric polymers as components. Other examples of components of BCPs include polyethylene oxide (PEO), polydimethylsiloxane (PDMS), poly-2-vinylpyridine (P2PV), poly-4-vinylpyridine (PS-P4VP), polyacrylate, polypropylene oxide (PPO), polyethylene, polyacrylonitrile (PAN), polylactide, polyacrylic acid (PAA), and polyisoprene. In some embodiments, a block copolymer can be chosen based on a desired chemical or functional characteristic of one or more components blocks, such as etch selectivity. Diblocks or higher order block copolymers can be used.
Block copolymer materials having various bulk morphologies may be used, including lamellae-forming block copolymers, cylinder-forming block copolymers, and sphere-forming block copolymers. Asymmetric and symmetric block copolymers can be used. The block copolymer material may include one or more additional block copolymers. In some embodiments, the material may be a block copolymer/block copolymer blend. The block copolymer material may also include one or more homopolymers.
The block copolymer material may include any swellable material. Examples of swellable materials include volatile and non-volatile solvents, plasticizers and supercritical fluids. In some embodiments, the block copolymer material contains nanoparticles dispersed throughout the material. The nanoparticles may be selectively removed.
As described above, in some embodiments, solvent annealing in the presence of chemical patterns can be leveraged to fabricate complex structures having a range of effective pattern periods. As such, in some embodiments, the block copolymer material includes a BCP without homopolymers and/or without other swellable materials. In some other embodiments, the block copolymer material may include a homopolymer or swellable material, for example, to increase commensurability tolerance.
As described above, the choice of solvent can depend on the block copolymer system and the desired morphology and dimensions of the assembled film. While the example of FIG. 3 uses a volatile solvent, in some embodiments, a non-volatile solvent that remains in the assembled film may be used. The solvent may be selective or non-selective to one or more of the components of the block copolymer material. At least one block of the block copolymer is typically soluble in the solvent. In some embodiments, a mixture of solvents may be used to achieve the desired characteristics, such as Lv, volume fraction, etc.
The solvent may be inorganic or organic. Examples of solvents include alcohols including methanol, ethanol, propanol, isopropanol, and butanol, ketones such as acetone. Further examples include tetrahydrofuran, acetone, dioxane, acetonitrile, dimethylsulfoxide, dimethylformamide, and carbon disulfide. In some embodiments, the solvent may be a mixture of two or more solvents.
EXPERIMENTAL
EXAMPLE 1
Effect of Solvent Choice on BCP Film Morphology and Period
30-nm-thick films of PS-b-P2VP (40k-b-40k) were coated on homogeneous substrates grafted by a series of PS-r-P2VP-r-PHEMA containing 41.8%-67.6% styrene and then annealed in acetone, N,N-dimethylformamide (DMF), toluene, carbon disulfide (CS2), and methanol for 16 h, 2 h, 9 h, 20 h, and 16 h respectively. 200-nm-thick films of PS-b-P2VP (40k-b-40k) on PS60.8%-r-P2VP-r-PHEMA brush were annealed in DMF and acetone for cross-sectional SEM imaging. PS-b-P2VP (40k-b-40k) thin films showed various morphologies and periods after being annealed in different solvent vapors.
PS-b-P2VP was chosen as an illustrative system since it is difficult for thermal annealing due to the large difference in surface tensions between PS and P2VP blocks, and it has relatively high Flory-Huggins interaction parameter (χ of about 0.217 at 20° C.).
Only micellar structure was observed on films annealed in methanol vapor. Toluene and CS2 vapor resulted in uneven films with fingerprint patterns on all brushes. The period Lv of the toluene solvated film and the CS2 solvated film was 57 and 63 nm, respectively. Annealing in DMF vapor for 2 h led to flat films with fingerprint patterns and a Lv of about 53 nm on PS-r-P2VP-r-PHEMA brushes containing ≧60.8% styrene. The cross-sectional SEM image (not shown) showed that the fingerprint patterns were composed of cylinders parallel to the substrate. After being annealed in acetone vapor, the PS-b-P2VP (40k-b-40k) films showed “island-hole” structures on all brushes except that fingerprint patterns with Lv of about 46 nm were observed on PS60.8%-r-P2VP-r-PHEMA grafted substrate as shown by the top-down SEM image (FIG. 11A). The film remained smooth after solvent annealing with a roughness rms=0.6 nm for a 2×2 μm2 area determined by an AFM height image (not shown). The cross-sectional SEM image (FIG. 11B) shows the formation of perpendicular lamellae, indicating that the PS60.8%-r-P2VP-r-PHEMA brush provides a non-preferential surface for the assembly of PS-b-P2VP (40k-b-40k) in acetone. It is noted that perpendicular lamellae are not obtained by thermal annealing this system.
All films were annealed in saturated solvent vapor for a time period long enough to reach fully swollen state. Depending on the nature of each solvent molecules, the swelling ratio of each block and the relative volume fraction may be greatly different, which may lead to different morphologies. Under thermal annealing, PS-b-P2VP (40k-b-40k) forms lamellae with L0 of 53 nm in bulk or in thin films. After being annealed in acetone vapor, PS-b-P2VP (40k-b-40k) also showed lamellae morphology, however, with period decreased by 13% in comparison to L0. Addition of a neutral non-selective solvent will tend to decrease the lateral spacing and thus decrease stretching normal to the interface, resulting in a reducing L0, while a strong selective solvent induces an increasing L0 since the chains stretch to reduce interfacial area. Without being bound by a particular theory, it is believed that a phase diagram for the PS-b-P2VP/acetone system may be similar to a symmetric poly(styrene-b-isoprene) (PS-b-PI) system in a selective solvent. At room temperature, the phase diagram for PS-b-PI shows the BCP morphology changing from lamellae, gyroid, cylinder, sphere, and then micelles upon increase of solvent fraction. For PS-b-P2VP, acetone is slightly selective for P2VP block and only swells the film by 41%, with the resulting BCP film retaining its lamellae morphology. The BCP films reached their immovable state while at least one block vitrified.
The results of acetone annealed films show the formation of perpendicular oriented lamellae and preferential wetting of the BCP films on the brushes. When PS-b-P2VP films are thermal annealed, the polymer-air free surface is preferentially wetted by the block with lower surface tension (PS block), which results in an orientation of the cylindrical or lamellar microdomains parallel to the surface. Here, perpendicularly oriented lamellae were obtained. This is likely due to the saturated vapor of acetone neutralizing the free interface. Unlike solvent/BCP systems in which highly-ordered BCP microdomains form at the top surface and propagate into the film as the solvent evaporates leading to perpendicular orientation, it is believed that the PS-b-P2VP/acetone system reaches quasi-equilibrium in its swollen state with its orientation governed by both the substrate and the free surface. In comparison to thermal annealed films, the composition of the non-preferential wetting brush for the symmetric BCP is slightly different due to the presence of solvent.
In situ film thickness measurements indicated that the adsorbed solvent evaporated quickly (within 3 s) after exposing the films to air. It is believed that the lateral dimensions do not change on fast evaporation, while uniaxial contraction along the direction normal to the substrate may occur. The dynamics of PS-b-P2VP (40k-b-40k) are too slow to reach an equilibrant state during rapid drying. Here, long-range ordered patterns of perpendicular lamellae formed on chemical patterns in the solvated films after a long time annealing with relatively low swelling ratio. Upon fast drying, the films only contracted in thickness, which did not affect the dimension of the perpendicular lamellae. These results are consistent with a quasi-equilibrium-and-quenching mechanism.
EXAMPLE 2
Chemical Patterning of and Solvent Annealing-induced Directed Assembly on 1:1 and 1:n Patterns
FIG. 12 is an example of a schematic illustration of processes used to create lithographically defined chemical patterns and subsequent solvent-vapor-induced directed assembly of BCP thin films. The preparation of 1:1 chemical patterns with Ls approximately equals to the period of the vitrified BCP domains Lv started with grafting PS—OH brush on silicon substrates. Then a layer of PMMA photoresist was applied and patterned with extreme ultraviolet interference lithography (EUV-IL). The chemical patterns were obtained by exposing the photoresist patterns to an O2 plasma and stripping the remaining photoresist in chlorobenzene. The chemical patterns with Ls approximately equal to nLv (n=2, 3, 4) were created on silicon substrates deposited with a thin layer of crosslinked PS (XPS) mats. A layer of PMMA photoresist was applied on the XPS mats with used EUV-IL and e-beam lithography to obtain grating patterns with Ls≈2Lv as illustrated. (Grating patterns with Ls≈3Lv and 4Lv were also obtained in this manner.) The photoresist patterns were then exposed to O2 plasma for extended time to trim the pattern lines to about 0.5 Lv in width and breakthrough XPS mat layer. After stripping the photoresist, PS51.5%-r-P2VP-r-PHEMA brush was grafted in the interspatial regions between XPS stripes for 1:2 chemical patterns. PS57.0%-r-P2VP-r-PHEMA brush was backfilled on 1:3 and 1:4 chemical patterns. Thin films of symmetric PS-b-P2VP (Mn=40.5-b-40.0 kg/mol) were spin coated on the chemical patterns.
The thin films were exposed to saturated acetone vapor for 14-20 h. FIG. 13 is a simplified schematic showing the experimental setup in which the BCP sample 1303 and solvent 1301 are sealed in a container 1305. Once removed from the container 1305, the absorbed solvent evaporates from the assembled BCP thin film. No significant difference was observed from samples with different annealing time in this time period.
The 30 nm thick PS-b-P2VP (40k-b-40k) films cast on chemical patterns with 40 nm≦Ls≦57.5 nm were annealed in acetone vapor and imaged by SEM, with the images shown in FIG. 7 and discussed above. The film assembled on Ls=45 nm pattern was also imaged by AFM (not shown). The smoothness of the assembled film was verified by the height image (roughness rms=0.8 nm for a 2×2 μm2 area). The solvent annealed BCP thin films are uniform throughout the entire prepatterned area (100 by 150 μm2). Directed assembly with high perfection is also shown in larger area images (10 μm long). Nearly perfect assembly occurs while Ls is commensurate to Lv.
Solvent annealing-induced two times density multiplication was demonstrated on a series of chemical patterns with 80 nm≦Ls≦110 nm, as discussed above with respect to FIG. 9. The uniformity of the solvent annealed films on the prepatterned area (25 by 150 μm2, Ls=90 nm), and the defect-free long-range order in larger area (10 μm long) was also observed in SEM images (not shown).
While lamellae-forming PS-b-PMMA has been directed to assemble on 1:n chemical patterns using PS43-50%-r-PMMA brush to backfill the interspatial region between XPS stripes, for the assembly of PS-b-P2VP via acetone annealing, a brush containing a higher styrene fraction (PS51.5%-r-P2VP-r-PHEMA) was used to backfill according to the higher styrene composition in the nonpreferential wetting brush (PS60.8%-r-P2VP-r-PHEMA) found in Example 1.
PS57.0%-r-P2VP-r-PHEMA brush was also used on 1:3 and 1:4 chemical patterns. Thin films of PS-b-P2VP (40k-b-40k) were spin-coated on the chemical patterns with Ls=138 nm (≈3Lv) and 184 nm (≈4Lv) and annealed in acetone vapor. As shown in FIG. 10, discussed above, the top-down SEM images indicate that triple and quadruple density multiplication on chemical patterns can also be induced by solvent annealing. Every third (Ls=138 nm) or fourth (Ls=184 nm) PS stripes are slightly wider than the others, which may be caused by the greater than 0.5L0 width of the underlying XPS stripes.
Solvent vapor induced BCP assembly on 1:1 chemical patterns was also demonstrated for thick films. Upon acetone annealing, two PS-b-P2VP (40-b-40) films with thickness of 147 and 235 nm (corresponding to about 3.2Lv and about 5.1Lv, respectively, with Lv about 46 nm) also displayed ordered and registered structures on chemical patterns. FIG. 14 shows top down SEM images of the films for Ls of 42.5, 45 nm, 47.5 and 50 nm. In comparison to the 30 nm film (FIG. 7) the commensurability tolerance decreased in the thicker films. Directed assembly with high perfection occurred only on Ls=45 and 47.5 nm prepatterns. On Ls=42.5 and 50 nm prepatterns, wavy lamellae with Lp close to L0 are observed. This may be due to the tilt of the lamellae to match with the wider surface pattern at the film-substrate interface. The registration of BCP patterns to the chemical patterns indicates the perpendicular orientation through the whole film thickness. This suggests that the ordering is induced by solvent evaporation at the film-substrate interface and not by (or just by) solvent evaporation at the film-air interface.
No top layer was observed in the solvent annealed PS-b-P2VP films. This is in contrast to thermal annealing, which often results in a thin top layer of PS on the PS-b-P2VP films due to the smaller surface tension of PS. It is believed that absence of the top PS layer is because the adsorbed solvent mediates the polymer-air interface energy.
One factor to achieve assembly on chemical patterns is the selective interaction between BCP blocks and the chemically patterned surface, for example, the selective wetting of PS and P2VP blocks on the PS brush and SiOx stripes respectively. During solvent annealing, the solvent to surface interaction may screen the interaction between BCP blocks and chemical patterns. The screening effect may increase with dilution of the BCP films. Therefore, the control of solvent volume fraction and the solvent selectivity may be used for the solvent annealing approach. Here, since acetone is a relatively poor solvent for PS block, relatively less acetone is absorbed in the PS domain, with the resulting interaction between the PS block and PS brush sufficient to induce directed self-assembly. The P2VP block, which contains more acetone, is flexible for the rearrangement of the BCP chains.
The results in Example 2 show that the BCP patterns register well to the chemical patterns, which suggests that the BCP assembly can be induced at the film-substrate interface by the interfacial interaction between the chemical patterns and BCP blocks. Although PS-b-P2VP has dissimilar surface tension (γs) between the PS and P2VP blocks, the solvent annealing approach can still produce long-range ordered perpendicularly oriented lamellae patterns that extend through the film thickness on both 1:1 and 1:n chemical patterns. The pattern quality and commensurability tolerance are comparable to those of poly(styrene-b-methyl methacrylate) (PS-b-PMMA) patterns induced by thermal annealing.
EXAMPLE 3
Directed Assembly of PS-b-PMMA Films by Solvent Annealing
Materials and Methods
Materials: PS-b-PMMA (Mn=52-52 and 95-92 kg/mol, polydispersity index (PDI)=1.10 and 1.06 respectively, Lo 50 nm and 80 nm, respectively), hydroxyl terminated PS (PS—OH, Mn=6.0 kg/mol, PDI=1.07), and hydroxyl terminated PMMA (PMMA-OH, Mn=6.3 kg/mol, PDI=1.06) were purchased from Polymer Source Inc. PMMA photoresist (Mn=950 kg/mol, 4 wt % in chlorobenzene) was purchased from MicroChem Inc. All solvents were purchased from Aldrich and used as received. Hydroxyl terminated poly(styrene-r-methyl methacrylate) (PS-r-PMMA-OH, Mn=12.5 kg/mol, PDI=1.25) was synthesized by nitroxide-mediated polymerization. The styrene fraction was determined to be 57 mol % by 1H NMR analysis. Crosslinkable PS (Mn=30.5 kg/mol, PDI=1.22) was synthesized by nitroxide-mediated copolymerization of styrene and glycidyl methacrylate and contained about 4 mol % of crosslinkable epoxy groups.
Substrate modification: 1 wt % toluene solutions of hydroxyl terminated polymers (PS—OH, PMMA-OH, or PS-r-PMMA-OH) were spin-coated on silicon wafers and annealed at 190° C. for 7 h under vacuum. The substrates were then sonicated in toluene to remove the non-grafted polymer, which yielded 3-4 nm thick imaging layers. While preparing substrates with crosslinked PS (XPS) layer, 0.2 wt % toluene solution of crosslinkable PS was spin-coated on silicon wafers and annealed at 190° C. for 24h under vacuum. Non-crosslinked PS was removed by sonication in toluene to form a XPS layer with a thickness of about 7 nm.
Fabrication of chemical patterns: A 70-nm-thick PMMA photoresist film was deposited onto the silicon substrates grafted with PS-OH or XPS and baked at 160° C. for 60 seconds. The photoresist patterns were exposed either by electron beam lithography (EBL) or extreme ultra-violet interference lithography (EUV-IL). EBL was performed on a LEO 1550 VP SEM equipped with a J. C. Nabity pattern generation system with an acceleration voltage of 20 kV. EUV-IL was carried out at the Synchrotron Radiation Center (SRC) at the University of Wisconsin-Madison using a transmission membrane interferometric mask. All patterns were exposed on PMMA resist and developed with a 1:3 (v:v) mixture of methyl isobutyl ketone:isopropanol (MIBK:IPA) for 60 seconds and rinsed with IPA. The 1:1 chemical patterns with alternative stripes of PS—OH (or XPS) and bare SiOx were obtained by O2 plasma etching and stripping the photoresist in chlorobenzene with sonication. The 1:2 chemical patterns were fabricated using resist patterns exposed on XPS-grafted substrate. The resist patterns were trimmed by extending O2 plasma etching time. After removal of the photoresist with chlorobenzene, a 20-nm-thick film of PS-r-PMMA-OH with 50 mol % of styrene content was spin-coated onto the patterned substrate. The substrate was then annealed at 19° C. for 4 hrs to graft the brush into the interfacial regions between the XPS stripes. Excess PS-r-PMMA-OH was removed by sonication in toluene to yield grating patterns of alternating XPS stripes with width of 1⁄2Lv and PS-r-PMMA stripes.
Solvent Annealing: Thin films of PS-b-PMMA were spin-coated on the substrates from a 1 wt % toluene solution. The samples were then placed in a sealed 20-mL vial along with an open 5-mL vial containing approximately 2 mL solvent. Solvent annealing was carried out at an ambient temperature of 22° C. for 1.5-46 hours. Identical vials and solvent containers were used for every experiment. After annealing, the samples were taken out of the vial and dried quickly in ambient atmosphere.
Scanning Electron Microscopy (SEM): A LEO 1550 VP field-emission SEM was used to image the BCP films using 1 kV acceleration voltage. The BCP films were imaged without PMMA block removal unless specified. The PMMA block was removed by exposure to UV light for 10 min, immersion into acetic acid for 2 min, and rinsing with deionized water.
Results
Ultra-thin films of PS-b-PMMA (95k-b-92k) were annealed in different solvent vapors. Micellar structures were observed from CS2 vapor and disordered wormlike morphologies from chlorobenzene and toluene vapors. Acetone was chosen as the annealing solvent due to its interesting property of inducing different BCP morphologies. The polymer-solvent interaction parameters are χPS-Acetone=1.1 and χPMMA-Acetone=0.29.
25-nm-thick PS-b-PMMA (95k-b-92k) films on unpatterned surfaces and chemical patterns were annealed in acetone for various times between 1.5 h and 46 h. The as-cast films showed disordered wormlike structures, with top down SEM images of the annealed films shown in FIG. 4 and discussed above.
PS-b-PMMA (95k-b-92k) films on unpatterned substrates grafted by PS—OH, PS57%-r-PMMA-OH, and PMMA-OH were annealed in acetone vapor for 1.5, 5, and 44 h. FIG. 15 shows top down SEM images. A similar change in morphology as is shown in FIG. 4 is observed for these surfaces.
Due to the lower surface tension of PS than that of PMMA, the as-cast films had a PS-rich layer at the top surface, verified by a 88° contact angle. The time dependent morphology transition can be explained by a mechanism involving the gradual migration of PMMA block to the top surface. Without being bound by a particular theory, it is believed that the migration may be driven by the stronger interaction between PMMA block and the solvent vapor. The BCP forms PMMA dots and stripes, with PS spheres forming as more PMMA block rises to the free surface.
FIG. 16 shows the directed assembly of PS-b-PMMA (95k-b-92k) on grating chemical patterns with Ls=70 nm, 80 nm, and 90 nm after 5 h acetone annealing. The SEM imaging direction was adjusted so that the stripes of chemical patterns are vertical in the images. For Ls=70 nm and 80 nm, commensurate with the Lv of 75 nm, all PMMA dots align in the direction parallel to chemical pattern stripes. The alignment reveals the directed assembly of the chemical patterns. The PMMA dots formed pseudo hexagonal patterns as shown by the inset 2D FFT images. On chemical patterns with Ls=90 nm, the alignment reduced.
Stripes were observed after 10 h acetone annealing. The directed assembly of these stripes were carried out on chemical patterns with Ls=60 nm-95 nm, with top-down SEM images shown in FIG. 17. On chemical patterns with Ls=60 and 65 nm, the stripes formed patterns with period Lp approximately equal to Lv and which were partially oriented in the direction of the prepatterns. Long-rang ordered and registered stripes were observed on Ls=70 nm, 75 nm, 80 nm, and 85 nm. The periods Lp of these perfect ordered stripes are consistent with the corresponding Ls. With increasing Ls of 90 nm and 95 nm, wavy BCP stripe patterns with Lp approximately equal to L0 were observed.
FIG. 18 shows top-down SEM images of the epitaxial assembly of PS-b-PMMA (95k-b-92k) films on grating chemical patterns with Ls=60-90 nm after exposure to acetone vapor for 46 h. All films showed a honeycomb microstructure, which changed to a rounded shape after PMMA removal (not shown). These PS hexagons were closely packed. Nearly perfect long-range ordered hexagonal patterns of PS hexagons were directed by chemical patterns with Ls=70 nm, 75 nm, and 80 nm. The PS hexagons were nearly symmetric at Ls=70 nm and 75 nm, although they were smaller at Ls=70 nm. The hexagons stretched in the direction normal to the chemical pattern stripes at Ls=80 nm.
Directed assembly of PS-b-PMMA (95k-b-92k) ultrathin films on irregular chemical patterns was investigated. 25-nm-thick BCP films were directed to assemble on nested arrays of lines (Ls=75 nm) with 60°, 90°, 120°, and 150° bends. The results are discussed above with respect to FIG. 8.
Symmetric PS-b-PMMA ultrathin films were also directed to assemble on 1:2 chemical patterns via solvent annealing. Well-defined 1:2 chemical patterns of XPS stripes with 0.5 Lv in width and backfilled with PS57%-r-PMMA-OH in the interspatial regions were fabricated. PS-b-PMMA (52k-b-52k) ultrathin films were annealed in acetone on the 1:2 patterns. Both PMMA dots and stripes were observed coexist after 1.5h, with 5h annealing resulting in stripe structures. The assembly took a shorter time for the smaller molecular weight BCP. The stripes of PS-b-PMMA (52k-b-52k) on PS—OH grafted silicon substrate had a vitrified BCP microdomain period, Lv, of 41 nm. A 80 nm chemical pattern directed nearly perfect assembly of the stripes with 2 times density multiplication. On chemical patterns with Ls=70 nm and 90 nm, only a small portion of the BCP stripes registered to the prepatterns. A fingerprint pattern was observed at Ls=100 nm.
Applications
Applications include pattern transfer as well as functionalizing one or more domains of the assembled block copolymer structure. Applications included nanolithography for semiconductor devices, fabrication of cell-based assays, nanoprinting, photovoltaic cells, and surface-conduction electron-emitter displays. In certain embodiments, patterned media and methods for fabricating pattern media are provided. The methods described herein may be used to generate the patterns of dots, lines or other patterns for patterned media. According to various embodiments, the resulting block copolymer films, nanoimprint templates, and patterned media disks are provided. In certain embodiments, a nanoimprint template is generated. A nanoimprint template is a substrate with a topographic pattern which is intended to be replicated on the surface of another substrate. There are several types of nanoimprinting processes. For UV-cure nanoimprinting, the template is a UV-transparent substrate (for example, made of quartz) with etched topographic features on one side. The patterned side of the template is brought into contact with a thin film of UV-curable liquid nanoimprint resist on the substrate to which the pattern is intended to be transferred. The liquid conforms to the topographic features on the template, and after a brief UV exposure, the liquid is cured to become a solid. After curing, the template is removed, leaving the solid resist with the replicated inverse topographic features on the second substrate. Thermal nanoimprinting is similar, except that instead of UV-light curing a liquid resist, heat is used to temporarily melt a solid resist to allow flow of the resist to conform with topographic features on the template; alternatively, heat can be used to cure a liquid resist to change it to a solid. For both approaches, the solid resist pattern is then used in subsequent pattern transfer steps to transfer the pattern to the substrate (or the resist may be used directly as a functional surface itself). The nanoimprint template may be generated by selectively removing one phase of the block copolymer pattern and replicating the topography of the remaining polymer material with a molding or nanoimprinting process. In certain embodiments, the nanoimprint template may be generated with one or more additional pattern transfer operations. A discussion of using an assembled BCP film to generate a nanoimprint template for patterned media applications is discussed, for example, in above-referenced US 2009-0196488, titled “Density Multiplication And Improved Lithography By Directed Block Copolymer Assembly.”
FIG. 19 is a process flow diagram illustrating operations in creating and using a BCP according to certain embodiments. First, a block copolymer film is directed to assemble on substrate with a chemical contrast pattern via solvent annealing (1901). This is done in accordance with the methods described above. One of the domains of the block copolymer film is then removed, e.g., by an oxygen plasma, thereby creating raised or recessed features (1903). The topographic pattern is then transferred to a substrate (1905). According to various embodiments, the pattern may be transferred by using the remaining polymer material as an etch mask for creating topography in the underlying substrate, or by replicating the topography in a second substrate, for example, by using a molding or nanoimprinting process.
The resulting structure can then be replicated by nanoimprinting, for example to create patterned media. The flow diagram shown in FIG. 19 is just an example of a process. In certain embodiments, the structure created by selective removal of one of the polymer phases in 1903 may be used as a template, e.g., after treating or functionalizing the remaining phase.
Although the foregoing invention has been described in some detail for purposes of clarity of understanding, it will be apparent that certain changes and modifications may be practiced within the scope of the invention. It should be noted that there are many alternative ways of implementing both the process and compositions of the present invention. Accordingly, the present embodiments are to be considered as illustrative and not restrictive, and the invention is not to be limited to the details given herein.

## Claims

1. A method comprising:
providing a substrate pattern;
depositing a block copolymer material on the substrate pattern; and
inducing the formation of microphase-separated domains in the block copolymer material by solvent annealing, wherein the substrate pattern has a pattern period (Ls) between 0.8 and 1.2 times a vitrified microdomain period of the block copolymer material in the solvent (Lv).

2. The method of claim 1, wherein Lv is not equal to the bulk period Lo of the block copolymer material.

3. The method of claim 1, wherein Lv is less than the bulk period Lo of the block copolymer material.

4. The method of claim 1, wherein Lv is greater than the bulk period Lo of the block copolymer material.

5. The method of claim 1, wherein the substrate pattern includes at least one feature having an effective pattern period that differs from Ls.

6. The method of claim 1, further comprising evaporating the solvent.

7. The method of claim 1, further comprising, prior to providing the substrate pattern, determining Lv.

8. The method of claim 1, wherein the solvent is selected from methanol, acetone, carbon disulfide, dimethylformamide, toluene, and tetrahydrofuran.

9. The method of claim 1, wherein all of the polymer blocks of the block copolymer material are soluble in the solvent.

10. The method of claim 1, wherein at least one of the polymer blocks of the block copolymer material is insoluble in the solvent.

11. The method of claim 1, wherein the microphase-separated domains are registered with the substrate pattern.

12. The method of claim 1, wherein the microphase-separated domains are oriented substantially perpendicular to the substrate.

13. The method of claim 12, wherein the microphase-separated domains extend through the entire thickness of the block copolymer material.

14. The method of claim 1, wherein Ls is between 0.9 Lv and 1.1Lv.

15. The method of claim 1, wherein the interaction parameter (χ) of a block copolymer in the block copolymer material is larger than that of PS-b-PMMA at the temperature of assembly.

16. The method of claim 1, wherein the solvent annealing is performed at room temperature.

17. A method comprising:
providing a block copolymer film on a substrate pattern;
exposing the block copolymer film on the substrate pattern to a solvent to thereby direct the assembly of the block copolymer film while the block copolymer film is in a solvated and microphase-separated state such that the block copolymer film has assembled domains having dimensions in x- and y-directions, the x- and y-directions being parallel to an underlying substrate; and,
after directing the assembly of the block copolymer film, evaporating the solvent such that the assembled domains are in a vitrified state, wherein the x- and y-dimensions of the assembled domains in the vitrified state are the same as the x- and y- dimensions of the assembled domains in the solvated state.

18. The method of claim 17, wherein the assembled block copolymer film has smaller features than the bulk block copolymer.

19. The method of claim 17, wherein the density of features in the assembled block copolymer film is greater than the substrate pattern density.