Ordered nanoscale domains by infiltration of block copolymers

Abstract

A method of preparing tunable inorganic patterned nanofeatures by infiltration of a block copolymer scaffold having a plurality of self-assembled periodic polymer microdomains. The method may be used sequential infiltration synthesis (SIS), related to atomic layer deposition (ALD). The method includes selecting a metal precursor that is configured to selectively react with the copolymer unit defining the microdomain but is substantially non-reactive with another polymer unit of the copolymer. A tunable inorganic features is selectively formed on the microdomain to form a hybrid organic/inorganic composite material of the metal precursor and a co-reactant. The organic component may be optionally removed to obtain an inorganic feature s with patterned nanostructures defined by the configuration of the microdomain.

Claims

1. A method of preparing an inorganic ordered nanoscale domain within a block copolymer, comprising: providing a block copolymer, the block copolymer including a first polymer free of a reactive functional group and a second polymer forming a plurality of ordered polymer nanoscale domains characterized by the reactive functional group and having a configuration; selectively binding a first gas metal precursor, comprising a first metal, to the reactive functional group within the plurality of ordered polymer nanoscale domains in a self-limited reaction; reacting a second gas precursor with the bound first gas metal precursor within the plurality of ordered polymer nanoscale domains and forming an inorganic feature comprising the first metal localized within the plurality of ordered polymer nanoscale domains within the block copolymer; and removing the block copolymer to obtain a plurality of the inorganic features having a structure defined by the configuration of the plurality of nanoscale domains prior to removal.

2. The method of claim 1, further comprising alternately exposing the block copolymer to the first gas metal precursor and the second gas precursor until the plurality of inorganic features achieve a desired dimension.

3. The method of claim 2, wherein a size-selective membrane is prepared using a porous inorganic membrane fabricated from SIS growth within a cylindrical or three-dimensional network comprising a bicontinuous structured block copolymer.

4. The method of claim 2, further comprising alternately exposing the block copolymer to a third gas metal precursor and a fourth gas precursor until the plurality of inorganic features achieve a desired dimension, wherein the third gas metal precursor includes a second metal substantially non-reactive with the reactive functional group.

5. The method of claim 1, wherein the reactive functional group is a carbonyl group, and wherein the inorganic feature comprises a material selected from the group consisting of: Trimethyl Aluminum (TMA), Yttrium Tris(2,2,6,6-Tetramethyl-3,5-Heptanedionate) (Y(thd)3), Diethyl Zinc (DEZ), Titanium tetrachloride (TiCl4), Vanadium (V) Oxytriisopropoxide (VOTP), Palladium (II) hexafluoroacetylacetonate (Pd(hfac)2), copper bis(2,2,6,6-tetramethyl-3,5-heptanedionate) (Cu(thd)2), copper(II) hexafluoroacetylacetonate hydrate (Cu(hfac)2), iron tris(2,2,6,6-tetramethyl-3,5-heptanedionate) (Fe(thd)3), cobalt tris(2,2,6,6-tetramethyl-3,5-heptanedionate) (Co(thd)3), Bis(2,2,6,6-tetramethyl-3,5-heptanedionato)barium triglyme adduct (Ba(thd)2.tri), Bis(cyclopentadienyl) ruthenium (Ru(cp)2), disilane (Si2H6), Tungsten Hexafluoride (WF6), Bis(N,N-diisopropylacetamidinato)copper(I) (Cu(DIA)), Nickel (II) acetylacetonate (Ni(acac)2), antimony pentachloride (SbCl5), niobium pentachloride (NbCl5), niobium pentethoxide (Nb(OEt)5), titanium isopropoxide (Ti(iOPr)4), tris(tetramethylcyclopentadienyl) cerium (III), cyclopentadienyl indium (InCp), tris(i-propylcyclopentadienyl) lanthanum (La(iPrCp)3), bis(cyclopentadienyl) magnesium (Mg(Cp)2), bis(cyclopentadienyl) nickel (NiCp2), (trimethyl) methylcyclopentadienylplatinum (IV) (Pt(MeCp)Me3), bis(pentamethylcyclopentadienyl) strontium (Sr(Me5Cp)2), tris(cyclopentadienyl) yttrium (YCp3), bis(cyclopentadienyl) dimethylzirconium (ZrCp2Me2), bis(methylcyclopentadienyl) methoxymethyl zirconium (ZrOMe), tetrakis(dimethylamino) tin (TDMASn), tetrakis(dimethylamino) zirconium (TDMAZr), tris(dimethylamino) aluminum (TDMAAI), iridium(III) acetylacetonate (Ir(acac)3), niobium pentafluoride (NbF5), ferrocene (FeCp2), cyclohexadiene iron tricarbonyl (FeHD(CO)3), tetrakis(dimethylamino) antimony (TDMASb), aluminum trichloride (AlCl3), niobium (V) iodide (NbI5), tin (IV) iodide (SnI4), Tris(tetramethylcyclopentadienyl)gadolinium(III) (Gd(Me4Cp)3), Bis(pentamethylcyclopentadienyl)barium 1,2-dimethoxyethane adduct (Ba(Me5Cp)2-DMA), Molybdenum Hexafluoride (MoF6), Tris(tert-pentoxy)silanol (TTPSi), Silicon tetrachloride (SiCl4), lithium tert-butoxide (Li(tOBu)), trimethyl indium (TMIn), trimethyl gallium (TMGa), and dimethyl cadmium (TMCd).

6. The method of claim 1, wherein the second precursor is selected from the group consisting of: water, hydrogen peroxide, nitrous oxide, oxygen, ozone, hydrogen, formaldehyde, trimethyl aluminum, ammonia, hydrazine, dimethyl hydrazine, diethyl hydrazine, methyl-ethyl hydrazine, hydrogen sulfide, trimethyl phosphite, trimethyl phosphate, silane, and disilane.

7. The method of claim 1, wherein the plurality of ordered polymer nanoscale domains' configuration is a plurality of cylinders or inverse cylinders and the plurality of inorganic features are a plurality of metal cylinders of the first metal.

8. The method of claim 7, further comprising arranging the plurality of metal cylinders as an array emitter or a field emitter.

9. The method of claim 7, wherein the plurality of metal cylinders form a three-dimensional electrical contact infiltrating organic semiconductor features.

10. The method of claim 1, wherein the plurality of inorganic features comprises Pt, Pd, or other catalytically active metal or metal oxide species arranged to form a catalyst.

11. The method of claim 5, further comprising purging the block copolymer scaffold with an inert gas after each exposure of the metal precursor and after each exposure of the second precursor.

12. The method of 1, wherein the block copolymer comprises polystyrene-block-poly (methyl methacrylate) (PS-b-PMMA) and the inorganic feature is a metal oxide.

13. The method of claim 1, wherein selectively binding the first gas metal precursor comprises diffusing the first gas metal precursor into the block copolymer.

14. The method of claim 1, wherein plurality of ordered polymer nanoscale domains are characterized by the configuration selected from the group consisting of: spheres, cylinders, lamellae and bicontinuous structures.

15. The method of preparing an inorganic ordered nanoscale domain within a block copolymer, wherein the plurality of inorganic features are solid.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIGS. 1a-1c represent a schematic depiction for templated synthesis of nanoscopic inorganic materials on a single-layer PS-b-PMMA substrate by SIS;

(2) FIGS. 2a-2f show field emission scanning electron microscope (FESEM) images of Al.sub.2O.sub.3 patterns formed on a PS-b-PMMA scaffold disposed on a silicon (Si) wafer formed by various iterations of SIS cycles of Al.sub.2O.sub.3 with an exposure/purge timing sequence (60/300/60/300 seconds) followed by an O.sub.2 plasma treatment to remove the PS-b-PMMA scaffold, with FIG. 2a showing 1 SIS cycle, FIG. 2b showing 2 SIS cycles, FIG. 2c showing 3 SIS cycles, FIGS. 2d and 2f showing 6 SIS cycles, and FIG. 2e showing 10 SIS cycles; FIG. 2f depicts a mixture of Al.sub.2O.sub.3 nano-posts and nanocylinders obtained from polymer domains with different orientations; and FIG. 2h is a plot of the concentration of Al obtained from energy dispersive X-ray spectroscopy (EDX) taken along the path depicted in FIG. 2g;

(3) FIG. 3 is a plot of cylinder diameter (depicted by black squares .square-solid.) and center-to-center cylinder spacing (depicted by black diamonds .diamond-solid.) with increasing Al.sub.2O.sub.3 SIS cycles and the corresponding Al.sub.2O.sub.3 features thickness (depicted by white squares ) on a separate Si wafer;

(4) FIGS. 4a and 4b are FESEM images of a pattern of TiO.sub.2 cylinders on a Si wafer, formed by 5 and 10 cycles, respectively, of TiO.sub.2 SIS; FIG. 4c is an atomic force microscopy (AFM) height image of the pattern resulting from 5 cycles of ZnO SIS on a PS-b-PMMA scaffold; FIG. 4d is an AFM height image resulting from 1 cycle of Al.sub.2O.sub.3 ALD followed by 3 cycles of ZnO SIS;

(5) FIG. 5a-5d are FESEM images of nanopatterns formed on a Si wafer templated by a PS-b-PMMA scaffold following 1 cycle of Al.sub.2O.sub.3 SIS followed by 10 cycles of tungsten (W) SIS (FIG. 5a); 1 cycle of Al.sub.2O.sub.3 SIS followed by 20 cycles of W ALD (FIGS. 5b-5c); and 2 cycles of Al.sub.2O.sub.3 SIS followed by 20 cycles of W SIS (FIG. 5d); and

(6) FIG. 6a-6b schematically depict the bonding interaction of TMA and TiCl.sub.4, respectively, with a carbonyl group disposed within a block copolymer scaffold.

DETAILED DESCRIPTION OF EMBODIMENTS

(7) The present invention provides molecular-level control for preparing inorganic patterned nanostructures of a broad variety of materials with tunable characteristic feature sizes and shapes by utilizing the capabilities of block copolymer self-assembly and the selective interaction of one or more metal precursors with particular polymer units of the block copolymer. The resulting materials have a number of potential uses, including photovoltaic devices, structural supports for a separation membrane in a battery, a fluid filtration membrane, filtering and/or guiding selected wavelengths of light, as active channel material in a transistor, as an array emitter or a field emitter, a three-dimensional electrical contact, and a catalyst. In photovoltaic devices, nanostructures comprised of light absorbers, charge separation materials, and/or charge transport materials can outperform analogous devices without nanostructuresthis is especially true in systems where bound excitons are formed such as in organic and hybrid organic/inorganic photovoltaics. The uniformity and tenability of spacing between nanostructures lends itself to separation and nanofiltration applications. Photonic crystals with uniformly spaced nanostructures are effective at manipulating and modulating light.

(8) In some embodiments, the method uses sequential infiltration synthesis (SIS), SIS is related to atomic layer deposition (ALD). In general, the SIS process involves exposing the patterned organic material layer to various gas phase precursors to synthesize inorganic features. SIS coats the surface of the organic material but also infiltrates into the bulk organic material as well by adjusting the gas phase exposure pressure and timing. The gas phase precursors are available for selection for SIS modification which are capable of forming inorganic components within a variety of organic materials. Examples of inorganic features prepared by SIS include Al.sub.2O.sub.3, TiO.sub.2, ZnO, SiO.sub.2, and W. The infiltration of the inorganic material may be confirmed by monitoring mass intake by quartz crystal microbalance or by detecting diffusion using cross-sectional analysis with EDX or other techniques.

(9) In some embodiments, the SIS method may include relatively long periods of gas phase exposure to precursors. For example, the SIS method may include a relatively long period of gas phase exposure to precursor A followed by a long period of exposure to precursor B (with a purging step in-between). In another embodiment, the method may include a series of short pulses of A followed by another series of short pulses of B (with a purging step in-between). In some embodiments, a series of short pulses may be combined with long periods of gas phase exposure to a precursor. In some embodiments, the total time of exposure to a precursor for a SIS cycle may be 5 to 25 times higher than the typical time for an ALD cycle. In some embodiments, the total time of exposure to a precursor for a SIS cycle may be 10 times higher than the typical time for an ALD cycle. In some embodiments, the SIS method may include use of high pressure to facilitate infiltration of the inorganic material.

(10) Various embodiments of the present invention utilize sequential infiltration synthesis (SIS), which is related to atomic layer deposition (ALD) to form patterned inorganic features in a block copolymer scaffold. In an embodiment, a block copolymer scaffold is exposed alternately to two reactive gases. The first reactive gas may be a metal precursor that is selectively reactive with a functional group present in one of the polymer units but absent from at least one of the other polymer units in the block copolymer. The metal precursor selectively binds (either covalently or non-covalently) to the functional group but is substantially non-reactive with one or more other polymers. Substantially non-reactive refers to no greater than 10% polymer/precursor reaction as compared with the reaction between the target polymer and precursor. The metal precursor is substantially non-reactive when the precursor does not bind to the polymer under a SIS reaction. The second reactive gas may be a co-reactantfor example, serving as a second precursor in a cyclethat is selectively reactive with the first precursor that is bound to the polymer unit. By way of example, the first reactive gas may be a ligated metal such as trimethyl aluminum (TMA) and the second reactive gas may be water. In some embodiments, a third precursor may be used.

(11) Block copolymers are molecules composed of two or more polymers connected with covalent bonds. For example, polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) is composed of polystyrene (PS) and poly(methyl methacrylate) (PMMA) covalently linked. By varying the preparation conditions of the block copolymer, these blocks will phase-separate and self organize into structures with ordered nanoscale domains in various configurations such as spheres or lamella. The characteristic shape and dimensions of these domains can be tuned via polymeric design. In some embodiments, the block copolymer includes a plurality of self-assembled periodic polymer nanostructures. The nanostructures such as cylinders assemble on their own into a repeated pattern, such as by phase separation, which can, in some cases, be directed or manipulated with external parameters such as temperature, solvent vapors, electric fields, mechanical forces, magnetic fields, flow, or surface topography.

(12) In general, on a scaffold surface with the correct chemical termination, the SIS process results in the growth of an inorganic features associated with the SIS precursors used. The inorganic features is an inorganic layer that may be between 0.2 nm to 500 nm in height. For example, an aluminum oxide (Al.sub.2O.sub.3) features may be formed on the scaffold surface using a TMA precursor and a water co-reactant precursor. However, where the appropriate chemical termination is absent from the scaffold surface the SIS of the precursors will be inhibited. By selecting the precursors to selectively react with only one of the block copolymer units, the SIS process will result in growth within that polymer component only. Thus, SIS using TMA and water precursors on a PS-b-PMMA scaffold results in growth of inorganic Al.sub.2O.sub.3 features almost exclusively within the PMMA component, to the exclusion of the PS component. In some embodiments, less than 10% of Al.sub.2O.sub.3 growth may be in the PS. The ALD precursors infiltrate molecular-scale voids in the block copolymer scaffold and attach (covalently or non-covalently) to the polymer chains to form an inorganic-organic hybrid composite material. For example, TMA will react with the oxygen species in the PMMA component but not with the PS, which is comprised solely of carbon and hydrogen. An inorganic feature, in this case an Al.sub.2O.sub.3 feature, substantially assumes the same ordered nanostructure/spacing as the block copolymer, although the width of individual domains can be further tuned using the number of SIS cycles. The composite coated polymer scaffold can be left intact, or the sample can be oxidized to remove the organic material, leaving only the inorganic SIS material but preserving the initial structure provided by the block copolymer in the inorganic component.

(13) In light of the broad range of selective chemistries between various metal precursors suitable for ALD/SIS and polymer units as well as the enormous library of block copolymers and ALD-related processes, patterned functional materials could be synthesized onto a broad range of scaffolds. The process may be generalized to designing the desired block copolymers in terms of materials and microdomain configuration (e.g., shape and dimensions) and selecting corresponding SIS precursors reactively compatible with the appropriate polymer units and characterized by the desired final material properties (e.g., electronic and/or photo response). The process may used in forming various inorganic materials, including a metal, metal oxide, a metal nitride, a metal sulfide or other metal chalcogenide, a metal carbide, or a metal phosphide. In various embodiments, a transparent conductive metal oxide such indium tin oxide (ITO) may be formed using ALD precursors known in the art.

(14) For example, following the present approach, various inorganic features have been selectively deposited within block copolymers, including the formation of ZnO, TiO.sub.2, and W features. These materials grow exclusively on the PMMA unit of the PS-b-PMMA via selective reaction with the carbonyl chemistry of the PMMA. However, the precursors associated with the features are non-reactive with PS, which has no carbonyl groups. For each material, the inorganic material assumes the self-assembled, periodic nanostructure of the PMMA within the copolymer scaffold. Thus, an inorganic material is selectively nanopatterned and an organic/inorganic hybrid composite material is formed.

(15) Although carbonyl functional groups are described as one example of a polymer component or reactive functional groups that may be utilized for selective inorganic material growth, a variety of different polymer units are available to interact with various metal precursors through various interactions, including metal-ligand coordination, covalent bonding, and other interactions. For example, the pyridine groups in polyvinylpyridine, a common block for BCPs, could be used to selectively bind various metal compounds including Al(CH.sub.3).sub.3, AlCl.sub.3, ZnCl.sub.2, CdCl.sub.2, etc., which may be used as precursors in ALD-related processes. Additionally, hydroxyl groups provided by polyacrylic acid, another common block for BCPs, could react with various metal precursors, including Al(CH.sub.3).sub.3, TiCl.sub.4, Zn(C.sub.2H.sub.5).sub.2, etc. to form covalent bonds.

(16) Two components are significant in driving the present processes to obtain particular material characteristics. The first component is the selective and self-limited reaction of a metal precursor such as TiCl.sub.4, SnCl.sub.4, AlCl.sub.3, Al(CH.sub.3).sub.3, etc., which are Lewis acids in this example, with strategically selected functional moieties in the BCP such as the carbonyl groups in PMMA microdomains. Once bound to the polymer, the grafted metal-ligands serve as nucleation sites for the second component, which is the inorganic material synthesis by SIS. Within each of these components, the reactions are controllable on the molecular level and the characteristic self-limited heterogeneous reactions provide macroscopic uniformity in principle.

(17) A broad range of organized nanomaterials with tunable dimensions can be synthesized from a BCP scaffold such as PMMA and an even more expansive range is available in the context of other BCP chemistries. To demonstrate this approach with a particular set of materials, organized Al.sub.2O.sub.3 and TiO.sub.2 nanocylinders with controllable dimensions were synthesized. Starting with a monolayer of AlOH seeds generated in the PMMA domain via Al.sub.2O.sub.3 SIS.

(18) FIG. 1 depicts a technique for patterning a plurality of inorganic nanoscale features onto a scaffold by performing SIS with a self-assembled PS-b-PMMA block copolymer features template. The term self-assembled refers to both spontaneous organization to the BCP into nanoscale domains such as PMMA cylinder within a PS matrix or directed or biased self assembly such as by the use of an electric field or a temperature/pressure gradient. At 10 a PS-b-PMMA scaffold 100 is provided on a process scaffold 101, which may be a Si wafer, and loaded into the ALD reactor. The PS-b-PMMA scaffold 100 comprises a plurality of orientated PMMA microdomains 102 having one or more defined configurations, cylinders in the depicted embodiment. The plurality of orientated PMMA microdomains 102 are disposed within a matrix of PS 103.

(19) At 11 the PS-b-PMMA scaffold 100 is exposed to a vapor of a metal precursor, which diffuses into the BCP features and selectively reacts specifically with carbonyl groups in the PMMA domains as depicted in FIG. 6A. The non-coordinated excess metal precursor is then removed from the domain by a purge step such as with high purity N.sub.2 to prevent non-self-limited, homogeneous reactions. The PS-b-PMMA scaffold 100 is then exposed to a co-reactant precursor such as water, which reacts with the coordinate metal precursor. The first monolayer of a coordinated metal precursor provides reactive sites for the subsequent SIS process, which selectively grows an inorganic material 104 within the active PMMA microdomains 102. As the SIS process operates in a self-limited heterogeneous surface reaction mode, the growth of materials in the PMMA microdomain 102 continues in bottom-up assembly fashion with molecular precision. At 12, the polymer template 100 may be removed by thermal annealing or plasma treatment or other process known in the art. The result is a patterned inorganic structure 105 that mimics the configuration of the original self-assembled PMMA microdomains 102.

(20) Because the assembly process of the present technique uses units on the polymer chains as the molecular template, the final domain size of the deposited inorganic material is mainly determined by a combination of the number of available reactive sites in the domain and the amount of material being assembled into the domain by SIS cycling, an SIS cycle comprising exposure of the scaffold to the metal precursor and the following co-reactant exposure. This combination of attributes offers significant flexibility in tuning the final feature size when compared with conventional methods. For example, the process is capable of fabricating features considerably narrower than the characteristic dimension of the scaffold template. Additionally, the separated heterogeneous surface reactions in this process greatly decrease the likelihood of uncontrollable overgrowth in undesired microdomains.

(21) With reference to FIGS. 2a-2e, a series of SEM images show patterned Al.sub.2O.sub.3 nanocylinders resulting from 1 (FIG. 2a), 2 (FIG. 2b), 3 (FIG. 2c), 6 (FIGS. 2d and 2f), and 10 (FIG. 2e) SIS cycles of Al.sub.2O.sub.3 with a PS-b-PMMA features over a silicon scaffold. The figures show the nanocylinders after the self-organized PS-b-PMMA BCP scaffold thin features were removed by O.sub.2 plasma treatment or by heating in air at 500 C. for 6 hours. The O.sub.2 plasma etching was performed at 50 W for 1 minute in a March CS-1701 plasma etcher.

(22) In some embodiments, sequential infiltration synthesis (SIS) can be utilized to provide the described stepwise growth. In certain embodiments, finely tuned processing conditions, complex composites and inorganic nanomaterials with tunable features of hierarchical scales can be synthesized for applications ranging from solar cells to lithium batteries to catalysis. In-situ diffusion and reaction studies using a quartz crystal microbalance (QCM) show that even though SIS is a self-limited stepwise growth process, the SIS process depends strongly on complex coupled diffusion and reaction processes, which differentiates it from traditional atomic layer deposition. For example, in-situ QCM data shows that for polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) block copolymer (BCP) features, the reactants diffuse to the reactive site in PMMA through PS domains. The PS domains, being unreactive to the precursors act as a highway for delivering those reactants and remain unobstructed throughout the SIS process. Because the reaction between metal precursor and PMMA influences the mobility of molecular chains of PMMA, the diffusion of metal precursors strongly deviates from the classic diffusion model derived from Fick's Law. In other words, the presence of the PS matrix allows for an alternative pathway for the inorganic material to infiltrate the BCP even after the diffusion pathways are blocked by repeated cycles.

(23) In one embodiment, by tuning the strength of the reaction between metal precursors and soft matter (e.g. polymers), the interface between the SIS-synthesized materials and soft matter can be precisely adjusted, as well as the final structure of the composites and templated inorganic materials. For example, poly (4-vinyl pyridine) presents strong coordination reaction with TiCl.sub.4 and Al(CH.sub.3).sub.3, which prevents further material diffusion into the polymer and results in hollow tubes and spheres. For PMMA scaffolds, the reaction between metal precursors and soft matter is not strong enough to block the diffusion of materials into the matrix of PMMA nanodomains, therefore, solid nanorods, nanowires, or nanoposts with precisely-controlled size can be generated.

Examples

(24) Polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA, M.sub.W=50,500/20,900) (Polymer Source, Inc.) was purified through Soxhlet extraction to remove excess PS homopolymer. BCP solutions were prepared in toluene (Fisher, 99.5%) with a concentration of 13 mg/mL. The PS.sub.485-b-PMMA.sub.201 block copolymer scaffold features were prepared by spin coating from a toluene solution onto cleaned silicon scaffolds with native SiO.sub.2. After deposition, PS-b-PMMA features were annealed at 250 C. for two hours in a tube furnace under a flowing Ar atmosphere, then cooled to room temperature to obtain self-assembled patterns. The in-plane PMMA cylinders were 303 nm in diameter, and the center-to-center lateral distance was 605 nm. These dimensions can be varied by adjusting the molecular weight of the constituent polymer blocks.

(25) The Al.sub.2O.sub.3 SIS process was performed using the SIS timing sequence: 60/300/60/300 seconds, where the first times represent first metal precursor trimethyl aluminum (Al(CH.sub.3).sub.3 TMA 96%) exposure, inert purge, second co-reactant precursor (water) exposure, and inert purge. Ultrahigh purity N.sub.2 (99.999%) was used as the purge gas and carrier gas with further purification by an inert gas filter (Aeronex Gatekeeper) before entering the reactor. All precursors were introduced into the ALD reactor at room temperature vapor. In order to remove moisture and achieve thermal equilibrium, the scaffolds were subjected to a 300 sccm N.sub.2 flow at 1 Torr for at least 30 minutes and then evacuated to less than 20 mTorr before commencing SIS.

(26) As depicted in FIGS. 2a-2e, each of the Al.sub.2O.sub.3 stripe patterns resemble the parallel-oriented cylindrical microdomains of PMMA that were present in the original PS-b-PMMA scaffold thin features. FIGS. 2a-2f show field emission scanning electron microscope (FESEM) images of Al.sub.2O.sub.3 patterns formed on a PS-b-PMMA scaffold disposed on a silicon (Si) wafer formed by various iterations of SIS cycles of Al.sub.2O.sub.3 with an exposure/purge timing sequence (60/300/60/300 seconds) followed by an O.sub.2 plasma treatment to remove the PS-b-PMMA scaffold, with FIG. 2a showing 1 SIS cycle, FIG. 2b showing 2 SIS cycles, FIG. 2c showing 3 SIS cycles, FIGS. 2d and 2f showing 6 SIS cycles, and FIG. 2e showing 10 SIS cycles. FIG. 2f depicts a mixture of Al.sub.2O.sub.3 nano-posts and nanocylinders obtained from polymer domains with different orientations Additionally, the spatially localized presence of Al was verified by energy dispersive X-ray spectroscopy (EDX) as illustrated in the plot of FIGS. 2g and 2h, which illustrate a concentration of Al disposed along the plurality of nanocylinders. Some of the PMMA features are oriented in the plane of the field and other are standing on one end and appear to be chains and dots in FIG. 2(f).

(27) Contraction of the polymer and aggregation of the Al.sub.2O.sub.3 nuclei during the O.sub.2 plasma etching process further explain the formation of Al.sub.2O.sub.3 cylinders. The diameter of the Al.sub.2O.sub.3 cylinders resulting from one TMA/H.sub.2O cycle is 8.481.54 nm, which is much smaller than the approximately 30 nm-wide PMMA domains in the BCP features but also much bigger than expected in view of the Al.sub.2O.sub.3 ALD growth rate on a planar surface (1.2 /cycle). According to the self-limiting behavior of reaction between TMA and carbonyl groups, the maximum number of TMA molecules coordinating to each PMMA domain is determined by the number of carbonyl groups, which is about 200 per PMMA chain in this case. Assuming all 200 carbonyl units are coordinated to TMA, the cylinder diameter resulting from the first TMA/H.sub.2O SIS cycle would be about 11.5 nm, which is slightly higher than the experimentally observed value. The actual smaller size of the Al.sub.2O.sub.3 cylinders is attributable to a reduction in the number of coordinated TMA molecules by steric effects of the ligands in grafted TMA and the polymer scaffold and folding of polymer chains. These mechanisms are further supported by the broken points (as indicated by the arrows in FIG. 2a) along the Al.sub.2O.sub.3 cylinders generated from a single TMA/H.sub.2O cycle. Significantly, the slightly smaller Al.sub.2O.sub.3 feature size relative to the theoretical value is indicative of a reaction templated by the carbonyl groups on the polymer chain; and the coordination process of TMA onto the carbonyl groups is indeed self-limited. These characteristics provide the desired molecular-level control of the present processes.

(28) With the AlOH nucleation sites formed in the first cycle through the coordination reaction between TMA and the carbonyl groups and the following hydrolysis reaction with H.sub.2O, traditional Al.sub.2O.sub.3 ALD chemistry could be performed to incorporate more AlO ligands into the domain in a self-limited layer-by-layer fashion. With increasing Al.sub.2O.sub.3 cycles, the diameter of the Al.sub.2O.sub.3 cylinders increases as deduced from FIGS. 2a-2e. After 10 cycles, the Al.sub.2O.sub.3 cylinder diameter increases to 30.82.7 nm, which is comparable to the original PMMA domain size. The Al.sub.2O.sub.3 cylinders become continuous for samples with more than 1 TMA/H.sub.2O cycle as evidenced by the absence of visible breaks in the cylinders depicted in FIGS. 2b-2e.

(29) With reference to FIG. 3, the cylinder diameters as well as the center-to-center spacings measured from the SEM images (FIGS. 2a-2e) are plotted against the number of cycles. The mean center-to-center value remains nearly constant, at about 60 nm, regardless of the number of cycles performed. This value is consistent with the center-to-center spacing between PMMA domains in the initial BCP thin features template, 60 nm5 nm.

(30) The linear dependence of the Al.sub.2O.sub.3 cylinder size on the number of cycles depicted in FIG. 3 highlights the capability of ALD to tune the inorganic feature size without changing the dimensions of the BCP template. This eliminates the need to prepare BCPs with different domain sizes to control the size of the nanostructure, therefore providing substantial flexibility and simplifying the process. The increase of Al.sub.2O.sub.3 cylinder diameter results directly from the addition of material into the PMMA domains with each cycle. Further, as seen from FIG. 3, the Al.sub.2O.sub.3 cylinder diameter at 10 cycles using 5 longer precursor exposure times (timing: 300/300/300/300 seconds) than the above described example (timing: 60/300/60/300) is nearly the same as the cylinder diameter obtained using the shorter precursor exposure times. This further demonstrates that Al.sub.2O.sub.3 in the PMMA domains is self limited. Lengthening the exposure time in the cycle from 60 s to 300 s did not have an appreciable impact on the feature size, i.e. the amount of inorganic layer formed. This also suggests that a reaction exposure of 60 seconds is near the saturation point of the growth; and 300 seconds of purge time is sufficient to prevent homogenous reactions.

(31) The slope of the line for cylinder diameter in FIG. 3 shows a growth rate of about 2 nm/cycle, which is 16 greater than the Al.sub.2O.sub.3 ALD growth rate of 1.2 /cycle on planar surfaces determined by ellipsometry from the Si witness samples (lower trace in FIG. 3), such as indicated by the open squares on FIG. 3. The higher growth rate in the polymer may be ascribed to the higher density of accessible reactive sites on the permeable three dimensional PMMA domains with respect to the solid, planar Si surface. On the other hand, the growth rate of Al.sub.2O.sub.3 cylinder diameters is smaller than the theoretical value (about 10 nm/cycle) obtained when assuming all AlOH sites in the polymer matrix are accessible to the following process. This indicates that steric hindrance from AlOH and polymer ligands limits the number of accessible AlOH sites. With an increasing number of cycles, the growth of AlO matrix from different AlOH seeds will start to coalesce to form a dense and impermeable AlO network. The growth rate of Al.sub.2O.sub.3 in the microdomain will then substantially match the growth rate on a solid Si wafer.

(32) In addition to the flexibility in material deposition, there is also flexibility regarding the morphology or configuration of the BCP template and, therefore, the ultimate configuration of the inorganic nanostructures. For instance, when the PMMA domains are oriented normal to the scaffold, Al.sub.2O.sub.3 nanoposts may be fabricated. FIG. 2f shows a plurality of nanoposts formed with a diameter of 22.62.8 nm, similar to the in-plane cylinder diameters of 222.2 nm observed elsewhere on the same sample. As such, the present processes could be extended to synthesize nanomaterials with any of the morphologies accessible to BCPs, even into three-dimensional matrices.

(33) In an embodiment, patterned TiO.sub.2 cylinders were prepared using TiO.sub.2 SIS at 135 C. onto self-assembled PS-b-PMMA BCP thin features. In the first SIS cycle, titanium tetrachloride (TiCl.sub.4, 99.9%) coordinates to the carbonyl groups as illustrated in FIG. 6b, and then H.sub.2O exposure, hydrolyzes the TiCl.sub.4 to form TiOH which serves as the reactive site for subsequent TiCl.sub.4/H.sub.2O SIS cycles.

(34) Organized patterns of TiO.sub.2 cylinders generated with 5 and 10 cycles of TiO.sub.2 SIS were visible under SEM as shown by FIGS. 4a and 4b, respectively. Further AFM measurements confirmed the clear patterns of TiO.sub.2 cylinders resulting from multiple SIS cycles. X-ray photoelectron spectroscopy (XPS) measurements also confirmed the presence of Ti on the sample surface. As shown in FIGS. 4a and 4b, the domains in light contrast are the TiO.sub.2 cylinders with diameters of 13.31.4 nm and 16.91.9 nm after 5 and 10 TiO.sub.2 SIS cycles, respectively. The TiO.sub.2 cylinders are smaller than the domain size of the PMMA (about 30 nm) and again indicate that the growth of the TiO.sub.2 is guided by the molecular template on the polymer chain. The center-to-center distances of the TiO.sub.2 cylinders are nearly identical for these two samples at 55.66.6 nm and 59.33.2 nm, respectively. These dimensions once again match the corresponding spacing between the PMMA domains. These results confirm that the TiO.sub.2 preserves the original pattern that was present in the PS-b-PMMA thin features template.

(35) In another embodiment, nanoscale ZnO patterns was prepared using SIS. An SIS of ZnO (DEZ, >95% Strem and H.sub.2O at 85 C. and 135 C. with the timing sequence: 300/300/300/300 seconds) was performed. If moisture is present in the PMMA domains, ZnO should form via the hydrolysis reaction between DEZ and H.sub.2O. However, inorganic features were not observed by SEM after 5 ZnO SIS cycles followed by O.sub.2 plasma treatment. The AFM height image shown in FIG. 5c indicates a subtle pattern, suggesting a small amount of largely non-selective growth induced by the weak interaction between DEZ and the carbonyl groups in the PMMA domains. This result indicates that a self limited coordination reaction between the metal precursor and the carbonyl groups on the polymer chains is necessary for seeding the subsequent molecular assembly process by SIS. Owing to the molecular-level engineering offered by this method, in situ synthesized AlOH sites in PMMA microdomains formed by treating PS-b-PMMA with 1 or 2 cycles of Al.sub.2O.sub.3 SIS may be utilized to seed the growth of other inorganic materials which do not have direct selective chemistry with pure PS-b-PMMA polymer, e.g., ZnO, MgO, SiO.sub.2, etc.

(36) In yet another embodiment, SIS of ZnO was performed in BCP after first seeding with 1-2 cycles of Al.sub.2O.sub.3 SIS. FIG. 4d shows the AFM image of the pattern resulting from 1 Al.sub.2O.sub.3 SIS cycle (timing: 60/300/60/300 seconds) followed by 3 ZnO SIS (DEZ/H.sub.2O) cycles (timing; 300/300/300/300 seconds). The pattern is clearer than the image shown in FIG. 4c. The difference of height of the cylinders shown in FIGS. 4c and 4d was confirmed with corresponding EDAX line scans. The lateral size of the cylinders was measured to be 19.43.2 nm and EDAX measurements confirmed the spatial localization of Zn.

(37) In another embodiment, the process was performed with tungsten (W) SIS at 85 C. onto AlOH seeded PS-b-PMMA scaffold thin features using SIS precursors tungsten hexafluoride WF.sub.6 and disilane Si.sub.2H.sub.6 (WF.sub.6, >99.9% and Si.sub.2H.sub.6 99.998%, Sigma-Aldrich). FIG. 5a shows the organized nanostructure formed from 1 Al.sub.2O.sub.3 ALD cycle followed by 10 W SIS cycles (timing 60/300/60/300 seconds) and an O.sub.2 plasma treatment. Compared with the nanofeatures resulting from 1 SIS Al.sub.2O.sub.3 cycle (FIG. 2a), the cylinder size is much larger (diameter 25.91.9 nm) and broken points are not observed. Due to the inhibited growth of SIS W on pure polymers, a control sample was prepared with 10 W SIS cycles but no Al.sub.2O.sub.3 SIS, which showed no detectable features by SEM.

(38) Nanocylinders of greater diameter may be generated by performing additional W SIS cycles, e.g., 20 cycles, as illustrated by FIGS. 5b and 5d. As observed in the SEM image in FIG. 5b, the cylinders (diameter 41.82.7 nm) have a smooth top surface and rougher structures along their sidewalls suggesting that the preferential reaction of W SIS on the surface of the PMMA domains compared with inside of the domains. This may be due to the relatively slow diffusion of the larger W SIS precursor (WF.sub.6), particularly with increasing numbers of SIS cycles which decrease the diameter of the polymer pores and voids. The rough edges of the nanocylinders are ascribed to island-growth behavior of the W with the SIS process. Nevertheless, the gap between the PMMA domains is clear, which indicates again that the W growth originates within the PMMA domains and progresses as a self-limited heterogeneous surface reaction.

(39) The presence of W was confirmed by XRF. Moreover, the conductivity of the PS-b-PMMA-AlOH nanocomposite on a SiO.sub.2/Si scaffold after 20 cycles of W SIS treatment became detectible by two-point I-V measurement, further supporting the incorporation of W metal. As shown in FIG. 5c, dense nanoposts with dimensions of 40.33.1 nm were also observed on the sample shown in FIG. 5b, which again confirms the applicability of the process for templating different morphologies of inorganic structures in BCPs. For the sample prepared with 2 cycles of Al.sub.2O.sub.3 and 20 cycles of W SIS, nanocylinder features with larger diameters (43.63.1 nm) were observed due to the greater density of AlOH sites. Although the nanocylinders resulting from 20 cycles of W are larger than the PMMA domain size, the center-to-center spacing of those features, which are 55.73.2 nm and 55.43.0 nm for samples with 1 and 2 cycles Al.sub.2O.sub.3 seeds, respectively, is consistent with the corresponding periodicity in the original PS-b-PMMA features.

(40) The present methods may be extended to include combining a block copolymer material incorporating a conjugated semiconducting polymer such as poly(3-hexylthiophene) (P3HT) with an SIS material that is a wide-band-gap semiconductor such as TiO.sub.2 or ZnO. The patterned nanostructure would offer a large surface area p-n junction for efficient separation of photo (solar) generated excitons. The composite material may be incorporated into organic-inorganic hybrid photovoltaics which could achieve enhanced efficiency. Other applications are recognizable to those of skill in the art and may range from photonic crystals to various membranes.

(41) The foregoing description of embodiments of the present invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the present invention to the precise form disclosed, and modifications and variations are possible in light of the above teachings or may be acquired from practice of the present invention. The embodiments were chosen and described in order to explain the principles of the present invention and its practical application to enable one skilled in the art to utilize the present invention in various embodiments, and with various modifications, as are suited to the particular use contemplated.