Patent Grant
11377548
This application claims the benefit under 35 USC 119(a) of Korean Patent Applications No. 10-2020-0046153 filed on Apr. 16, 2020, and No. 10-2021-0046882 filed on Apr. 12, 2021, in the Korean Intellectual Property Office, the entire disclosures of which are incorporated herein by reference for all purposes.
The present disclosure relates to a 2-dimensional polymer nanosheet, and width, length, and height tunable method of preparing the same.
Two-dimensional (2D) organic/polymeric nanosheets have attracted tremendous attention due to their unique properties arising from their ultra-thin and flat morphology. For instance, semi-conducting 2D materials such as graphene show optoelectronic properties that have been applied in the fields of sensors, electronic transfer platforms, and photovoltaic cells. To prepare such functional 2D nanostructures by solution process, self-assembly of semi-crystalline block copolymers (BCPs) containing a solubilizing amorphous block is one of the most powerful and facile way to achieve various morphologies including rectangles, hexagons, diamonds, and squares. Their core crystalline blocks can be varied from non-conjugated polymers, such as poly-(ferrocenyl dimethylsilane) (PFS), poly(lactic acid) (PLLA), poly(ε-caprolactone) (PCL), and polyethylene (PE), to conjugated ones, including poly(3-hexylthiophene) (P3HT), and poly(para-phenylenevinylene) (PPV).
Since the properties of these nanomaterials are size-dependent, there have been numerous efforts to develop strategies including simple blending and heating to modulate their sizes, shapes, and dimensions. In particular, the most powerful and widely utilized method is crystallization-driven self-assembly (CDSA), creating uniform one-dimensional (1D) and 2D nanomaterials. Taking advantage of their living polymerization-like process, preparing even more complex block comicelles is possible. However, unlike inorganic or small organic molecules, semi-crystalline polymers undergo chain-folding during CDSA. In the case of 2D nanosheets, this leads to radial growth of 2D lamellae, such that the aspect ratio can be predicted, but the current technology does not allow for precise control of the length. In particular, for semi-conducting 2D nanosheets, there is another limitation in that the strong π-π interaction of the conjugated polymers lowers the solubility of the 2D nanostructures, resulting in irregular aggregation and uncontrolled self-assembly. While some problems may be solved by synthesizing BCPs containing non-conjugated shell blocks, these insulating blocks further limit the potential of the 2D nanosheets as electronic materials.
Despite the current success in controlling 2D nanostructures, understanding the 2D crystallization process in solution is still in its infancy. This application is of great importance as it allows the design of new polymers, broadening the scope of 2D nanostructures. To this end, the Manners group recently reported a growth kinetic study on the formation of 1D nanofibers. They observed that the conformational effect from the amorphous shell block of the BCPs disturbed the self-assembly process so that the kinetics were more complicated than those of analogous living polymerization and assembly of small molecules. In order to obtain a clear kinetic study, controlled self-assembly of homopolymers is required to eliminate this conformational effect of BCPs. However, CDSA from homopolymers without a stabilizing shell block is extremely challenging, with only a few successes reported by the Manners group, who used a novel strategy of introducing a charged end group into homopolymers, thereby inducing electrostatic repulsion. Due to these limitations, the kinetics of polymer self-assembly, especially quantitative 2D growth, have not been studied yet.
In view of the foregoing, the present disclosure provides a 2-dimensional polymer nanosheet, and width, length, and height tunable method of preparing the same.
However, problems to be solved by the present disclosure are not limited to the above-described problems. Although not described herein, other problems to be solved by the present disclosure can be clearly understood by those skilled in the art from the following descriptions.
A first aspect of the present disclosure provides a 2-dimensional polymer nanosheet, including a block copolymer represented by the following Chemical Formula 1 or the following Chemical Formula 2; and a homopolymer represented by the following chemical formula 3:
wherein, in the above Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3, each of R1 to R3 is independently, a substituted or unsubstituted, linear or branched C1-8 alkyl group, when at least one from R1 to R3 is substituted, it is substituted by —SiRaRbRc, each of Ra, Rb, and Rc is independently a linear or branched C1-4 alkyl group, each of m and o is independently an integer of 20 to 70, each of n and p is independently an integer of 5 to 70, and q is an integer of 5 to 70.
A second aspect of the present disclosure provides a method of preparing a 2-dimensional polymer nanosheet according to the first aspect of the present disclosure, including:
(a) mixing a block copolymer represented by the following Chemical Formula 1 or the following Chemical Formula 2, and a homopolymer represented by the following Chemical Formula 3 to obtain a 2-dimensional seed; and (b) adding an unimer including the homopolymer represented by the following Chemical Formula 3 to the 2-dimensional seed to obtain a 2-dimensional polymer nanosheet:
wherein, in the above Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3, each of R1 to R3 is independently, a substituted or unsubstituted, linear or branched C1-8 alkyl group, when at least one from R1 to R3 is substituted, it is substituted by —SiRaRbRc, each of Ra, Rb, and Rc is independently a linear or branched C1-4 alkyl group, each of m and o is independently an integer of 20 to 70, each of n and p is independently an integer of 5 to 70, and q is an integer of 5 to 70.
A third aspect of the present disclosure provides a device, including a 2-dimensional polymer nanosheet according to the first aspect of the present disclosure.
In exemplary embodiments of the present disclosure, the inventors successfully prepared uniform semi-conducting 2D sheets without stacking by blending strategy. Living crystallization-driven self-assembly (CDSA) was achieved by adding the homopolymer as a unimer to the prepared initial 2D seed by the preparing method. Interestingly, unlike typical 2D CDSA examples showing radial growth, this homopolymer assembled only in one direction. Owing to this uniaxial growth, the lengths of the 2D nanosheets could be precisely tuned from 1.5 to 8.8 μm with narrow dispersity according to the unimer-to-seed ratio. The inventors also studied the growth kinetics of the living 2D CDSA and confirmed first-order kinetics. Subsequently, the inventors prepared several 2D block comicelles (BCMs) using unimers with various molecular weight, including penta-BCMs in a one-shot method.
In exemplary embodiments of the present disclosure, in the process of preparing the 2D seed, a second solvent (co-solvent) different from a first solvent may be added to tune the width and/or length of the 2D seed formed according to the addition ratio of the second solvent. In addition, the length of the finally formed 2D nanosheet is tunable according to the U/S (unimer-to-seed) ratio of the unimer. Lastly, according to the molecular weight, i.e. the degree of polymerization, of the unimer, it is possible to form a block comicelle with various heights.
In the detailed description that follows, embodiments are described as illustrations only since various changes and modifications will become apparent to those skilled in the art from the following detailed description. The use of the same reference numbers in different figures indicates similar or identical items.
According to examples of the present disclosure,
According to examples of the present disclosure,
According to examples of the present disclosure,
According to examples of the present disclosure,
Hereinafter, examples of the present disclosure will be described in detail with reference to the accompanying drawings so that the present disclosure may be readily implemented by those skilled in the art. However, it is to be noted that the present disclosure is not limited to the examples but can be embodied in various other ways. In drawings, parts irrelevant to the description are omitted for the simplicity of explanation, and like reference numerals denote like parts through the whole document.
Through the whole document, the term “connected to” or “coupled to” that is used to designate a connection or coupling of one element to another element includes both a case that an element is “directly connected or coupled to” another element and a case that an element is “electronically connected or coupled to” another element via still another element.
Through the whole document, the term “on” that is used to designate a position of one element with respect to another element includes both a case that the one element is adjacent to the other element and a case that any other element exists between these two elements.
Further, through the whole document, the term “comprises or includes” and/or “comprising or including” used in the document means that one or more other components, steps, operation and/or existence or addition of elements are not excluded in addition to the described components, steps, operation and/or elements unless context dictates otherwise.
Through the whole document, the term “about or approximately” or “substantially” is intended to have meanings close to numerical values or ranges specified with an allowable error and intended to prevent accurate or absolute numerical values disclosed for understanding of the present disclosure from being illegally or unfairly used by any unconscionable third party.
Through the whole document, the term “step of” does not mean “step for”.
Through the whole document, the term “combination of” included in Markush type description means mixture or combination of one or more components, steps, operations and/or elements selected from a group consisting of components, steps, operation and/or elements described in Markush type and thereby means that the disclosure includes one or more components, steps, operations and/or elements selected from the Markush group.
Through this whole specification, a phrase in the form “A and/or B” means “A or B, or A and B”.
Through the whole document, the term “alkyl” includes linear or branched alkyl groups having 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 5 carbon atoms, or 1 to 4 carbon atoms and all the possible isomers thereof. For example, the alkyl group may include methyl group (Me), ethyl group (Et), n-propyl group (nPr), iso-propyl group (iPr), n-butyl group (nBu), iso-butyl group (iBu), tert-butyl group (tBu), sec-butyl group (sBu), n-pentyl group (nPe), iso-pentyl group (isoPe), sec-pentyl group (secPe) tert-pentyl group (tPe), neo-pentyl group (neoPe), 3-pentyl group, n-hexyl group, iso-hexyl group, heptyl group, 4,4-dimethyl pentyl group, octyl group, 2,2,4-trimethyl pentyl group, nonyl group, decyl group, undecyl group, dodecyl group, and isomers thereof, but may not be limited thereto.
Hereinafter, embodiments and examples of the present disclosure will be described in detail with reference to the accompanying drawings. However, the present disclosure may not be limited to the following embodiments, examples, and drawings.
A first aspect of the present disclosure provides a 2-dimensional polymer nanosheet, including a block copolymer represented by the following Chemical Formula 1 or the following Chemical Formula 2; and a homopolymer represented by the following chemical formula 3:
wherein, in the above Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3, each of R1 to R3 is independently, a substituted or unsubstituted, linear or branched C1-8 alkyl group, when at least one from R1 to R3 is substituted, it is substituted by —SiRaRbRc, each of Ra, Rb, and Rc is independently a linear or branched C1-4 alkyl group, each of m and o is independently an integer of 20 to 70, each of n and p is independently an integer of 5 to 70, and q is an integer of 5 to 70.
In an exemplary embodiment of the present disclosure, each of R1 and R3 may be independently, substituted or unsubstituted, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, sec-pentyl, 3-pentyl, iso-pentyl, tert-pentyl, neo-pentyl, sec-isopentyl, 2-methylbutyl, n-hexyl, sec-hexyl, 3-hexyl, iso-hexyl, tert-hexyl, sec-isohexyl, 3-isohexyl, 2-methylpentyl, 3,3-dimethylbutyl, 3-ethylbutyl, 2,2-dimethylbutyl, n-heptyl, iso-heptyl, neo-heptyl, tert-heptyl, sec-heptyl, n-octyl, iso-octyl, or 2-ethylhexyl, but may not be limited thereto. In an exemplary embodiment of the present disclosure, each of R1 and R3 is independently, substituted or unsubstituted, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, sec-pentyl, 3-pentyl, iso-pentyl, tert-pentyl, neo-pentyl, sec-isopentyl, 2-methylbutyl, or n-hexyl.
In an exemplary embodiment of the present disclosure, R2 may be, substituted or unsubstituted, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, 3-pentyl, iso-pentyl, tert-pentyl, neo-pentyl, sec-isopentyl, 2-methylbutyl, n-hexyl, sec-hexyl, 3-hexyl, iso-hexyl, tert-hexyl, sec-isohexyl, 3-isohexyl, 2-methylpentyl, 3,3-dimethylbutyl, 3-ethylbutyl, or 2,2-dimethylbutyl, but may not be limited thereto. In an exemplary embodiment of the present disclosure, R2 may be 3,3-dimethylbutyl or trimethylsilylethyl.
In an exemplary embodiment of the present disclosure, —SiRaRbRc may be —SiMe3, —SiEt3, —SiPr3, —SiBu3, —SiEtMe2, —SiEt2Me, —SiMe2Pr, —SiMePr2, —SiBuMe2, —SiBu2Me, —SiEt2Pr, —SiEtPr2, —SiBuEt2, —SiBu2Et, —SiBuPr2, or —SiBu2Pr.
In an exemplary embodiment of the present disclosure, a width (100) of the 2-dimensional polymer nanosheet may be about 100 nm to about 10 μm, but may not be limited thereto. For example, the width (100) of the 2-dimensional polymer nanosheet may be about 100 nm to about 10 μm, about 100 nm to about 5 μm, about 100 nm to about 1 μm, about 100 nm to about 900 nm, about 100 nm to about 800 nm, about 100 nm to about 700 nm, about 100 nm to about 600 nm, about 100 nm to about 500 nm, about 100 nm to about 400 nm, about 100 nm to about 300 nm, about 100 nm to about 200 nm, about 200 nm to about 10 μm, about 200 nm to about 5 μm, about 200 nm to about 1 μm, about 200 nm to about 900 nm, about 200 nm to about 800 nm, about 200 nm to about 700 nm, about 200 nm to about 600 nm, about 200 nm to about 500 nm, about 200 nm to about 400 nm, about 200 nm to about 300 nm, about 300 nm to about 10 μm, about 300 nm to about 5 μm, about 300 nm to about 1 μm, about 300 nm to about 900 nm, about 300 nm to about 800 nm, about 300 nm to about 700 nm, about 300 nm to about 600 nm, about 300 nm to about 500 nm, about 300 nm to about 400 nm, about 400 nm to about 10 μm, about 400 nm to about 5 μm, about 400 nm to about 1 μm, about 400 nm to about 900 nm, about 400 nm to about 800 nm, about 400 nm to about 700 nm, about 400 nm to about 600 nm, about 400 nm to about 500 nm, about 500 nm to about 10 μm, about 500 nm to about 5 μm, about 500 nm to about 1 μm, about 500 nm to about 900 nm, about 500 nm to about 800 nm, about 500 nm to about 700 nm, about 500 nm to about 600 nm, about 600 nm to about 10 μm, about 600 nm to about 5 μm, about 600 nm to about 1 μm, about 600 nm to about 900 nm, about 600 nm to about 800 nm, about 600 nm to about 700 nm, about 700 nm to about 10 μm, about 700 nm to about 5 μm, about 700 nm to about 1 μm, about 700 nm to about 900 nm, about 700 nm to about 800 nm, about 800 nm to about 10 μm, about 800 nm to about 5 μm, about 800 nm to about 1 μm, about 800 nm to about 900 nm, about 900 nm to about 10 μm, about 900 nm to about 5 μm, about 900 nm to about 1 μm, about 1 μm to about 10 μm, about 1 μm to about 5 μm, or about 5 μm to about 10 μm, but may not be limited thereto.
In an exemplary embodiment of the present disclosure, a length (010) of the 2-dimensional polymer nanosheet may be about 500 nm to about 20 μm, but may not be limited thereto. For example, the length (010) of the 2-dimensional polymer nanosheet may be about 500 nm to about 20 μm, about 500 nm to about 15 μm, about 500 nm to about 10 μm, about 500 nm to about 5 μm, about 500 nm to about 1 μm, about 500 nm to about 900 nm, about 500 nm to about 800 nm, about 500 nm to about 700 nm, about 500 nm to about 600 nm, about 600 nm to about 20 μm, about 600 nm to about 15 μm, about 600 nm to about 10 μm, about 600 nm to about 5 μm, about 600 nm to about 1 μm, about 600 nm to about 900 nm, about 600 nm to about 800 nm, about 600 nm to about 700 nm, about 700 nm to about 20 μm, about 700 nm to about 15 μm, about 700 nm to about 10 μm, about 700 nm to about 5 μm, about 700 nm to about 1 μm, about 700 nm to about 900 nm, about 700 nm to about 800 nm, about 800 nm to about 20 μm, about 800 nm to about 15 μm, about 800 nm to about 10 μm, about 800 nm to about 5 μm, about 800 nm to about 1 μm, about 800 nm to about 900 nm, about 900 nm to about 20 μm, about 900 nm to about 15 μm, about 900 nm to about 10 μm, about 900 nm to about 5 μm, about 900 nm to about 1 μm, about 1 μm to about 20 μm, about 1 μm to about 15 μm, about 1 μm to about 10 μm, about 1 μm to about 5 μm, about 5 μm to about 20 μm, about 5 μm to about 15 μm, about 5 μm to about 10 μm, about 10 μm to about 20 μm, about 10 μm to about 15 μm, or about 15 μm to about 20 μm, but may not be limited thereto.
In an exemplary embodiment of the present disclosure, a height of the 2-dimensional polymer nanosheet may be about 1 nm to about 500 nm, but may not be limited thereto. For example, the height of the 2-dimensional polymer nanosheet may be about 1 nm to about 500 nm, about 1 nm to about 400 nm, about 1 nm to about 300 nm, about 1 nm to about 200 nm, about 1 nm to about 100 nm, about 1 nm to about 50 nm, about 1 nm to about 10 nm, 10 nm to about 500 nm, about 10 nm to about 400 nm, about 10 nm to about 300 nm, about 10 nm to about 200 nm, about 10 nm to about 100 nm, about 10 nm to about 50 nm, 50 nm to about 500 nm, about 50 nm to about 400 nm, about 50 nm to about 300 nm, about 50 nm to about 200 nm, about 50 nm to about 100 nm, 100 nm to about 500 nm, about 100 nm to about 400 nm, about 100 nm to about 300 nm, about 100 nm to about 200 nm, about 200 nm to about 500 nm, about 200 nm to about 400 nm, about 200 nm to about 300 nm, about 300 nm to about 500 nm, about 300 nm to about 400 nm, or about 400 nm to about 500 nm, but may not be limited thereto.
In an exemplary embodiment of the present disclosure, the 2-dimensional polymer nanosheet may have conductivity and/or fluorescence.
A second aspect of the present disclosure provides a method of preparing a 2-dimensional polymer nanosheet according to the first aspect of the present disclosure, including:
(a) mixing a block copolymer represented by the following Chemical Formula 1 or the following Chemical Formula 2, and a homopolymer represented by the following Chemical Formula 3 to obtain a 2-dimensional seed; and (b) adding an unimer including the homopolymer represented by the following Chemical Formula 3 to the 2-dimensional seed to obtain a 2-dimensional polymer nanosheet:
wherein, in the above Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3, each of R1 to R3 is independently, a substituted or unsubstituted, linear or branched C1-8 alkyl group, when at least one from R1 to R3 is substituted, it is substituted by —SiRaRbRc, each of Ra, Rb, and Rc is independently a linear or branched C1-4 alkyl group, each of m and o is independently an integer of 20 to 70, each of n and p is independently an integer of 5 to 70, and q is an integer of 5 to 70.
Detailed descriptions on the second aspect of the present disclosure, which overlap with those on the first aspect of the present disclosure, are omitted hereinafter, but the descriptions of the first aspect of the present disclosure may be identically applied to the second aspect of the present disclosure, even though they are omitted hereinafter.
In an exemplary embodiment of the present disclosure, in (a), the 2-dimensional seed may be formed by co-assembly of the block copolymer and the homopolymer.
In an exemplary embodiment of the present disclosure, in (b), the 2-dimensional polymer nanosheet may be formed by seeded-growth.
In an exemplary embodiment of the present disclosure, (a) may be conducted in presence of a first solvent, and in (a), a width of the 2-dimensional seed may be tunable by adding a second solvent different from the first solvent. Here, the first solvent may be at least one selected from chloroform, dichloromethane, and tetrahydrofuran, and wherein the second solvent may be at least one selected from methyl chloride, dichloromethane (DCM; or methylene chloride, MC), chloroform, tetrahydrofuran, toluene, chlorobenzene, dichlorobenzene, and o-dichlorobenzene, but may not be limited thereto. In an exemplary embodiment of the present disclosure, the first solvent may be chloroform, and the second solvent may be dichloromethane.
In an exemplary embodiment of the present disclosure, the width of the 2-dimensional seed may be adjusted according to the added amount of the second solvent. In particular, the width of the 2-dimensional seed may be adjusted according to the volume ratio of the second solvent.
In an exemplary embodiment of the present disclosure, in (b), a length of the 2-dimensional polymer nanosheet may be tunable according to the weight ratio of the unimer to the 2-dimensional seed.
In an exemplary embodiment of the present disclosure, in (b), a height of the 2-dimensional polymer nanosheet may be tunable according to degree of polymerization of the added unimer. Here, a block comicelle may be formed by adding at least two unimers of which degree of polymerization is different to each other, but may not be limited thereto. For example, a penta-block comicelle may be formed by adding two unimers of which degree of polymerization is different to each other.
In an exemplary embodiment of the present disclosure, the at least two unimers of which degree of polymerization is different to each other may be added simultaneously or sequentially, but may not be limited thereto. Here, even if the unimers are added simultaneously, the seeded-growth of one type of unimer takes place preferentially, so that the block comicelle can be formed in a one-shot method.
In an exemplary embodiment of the present disclosure, the method may further include a heating step and/or an aging step in (a) and/or (b), but may not be limited thereto. In an exemplary embodiment of the present disclosure, in (a), the block copolymer represented by Chemical Formula 1 or Chemical Formula 2, and the homopolymer represented by Chemical Formula 3 may be mixed, heated and then aged. In an exemplary embodiment of the present disclosure, in (b), the unimer including the homopolymer represented by Chemical Formula 3 may be added to the 2-dimensional seed, and then aged.
A third aspect of the present disclosure provides a device, including a 2-dimensional polymer nanosheet according to the first aspect of the present disclosure.
Detailed descriptions on the third aspect of the present disclosure, which overlap with those on the first and second aspects of the present disclosure, are omitted hereinafter, but the descriptions of the first and second aspects of the present disclosure may be identically applied to the third aspect of the present disclosure, even though they are omitted hereinafter.
In an exemplary embodiment of the present disclosure, the two-dimensional polymer nanosheet of the present disclosure may be included and/or applied without limitation as long as the device is a device using electrical/thermal conductivity and/or fluorescence of the two-dimensional polymer nanosheet of the present disclosure.
In an exemplary embodiment of the present disclosure, the device is transistor, sensor, imaging agent, light emitting diode, photovoltaic cell, or conductive display, but may not be limited thereto.
Hereinafter, example embodiments are described in more detail by using Examples, but the present disclosure may not limited to the Examples.
Without additional notes, all reagents were commercially available from Sigma-Aldrich, Tokyo Chemical Industry Co. Ltd., Acros Organics, Alfa Aesar and were used without further purification. Solvents for monomer synthesis were also commercially available, but they for polymerization are used after further-distillation under Ar(g). All the reactions were conducted under the Ar(g), and monitored by thin-layer chromatography carried out on pre-coated plates (MERCK TLC silica gel 60, F254). For purification, flash column chromatography was performed using MERCK silica gel 60 (0.040˜0.063 mm). For polymerization, the Grubbs third-generation (G3) catalyst was prepared following the reported literature.
Polymers
(1) Polymerization Procedure
A 4 mL sized screw-cap vial with septum was flame dried and charged with a monomer and a magnetic bar. The vial was purged with Ar(g) three times, and degassed anhydrous THF was added (M1: a monomer of P1, M2: a monomer of P2, [M1]0=0.5 M or [M2]0=0.1 M). After the Ar(g)-purged G3 catalyst in the other 4 mL vial was dissolved in 50 μL THF, the solution was rapidly injected to the monomer solution at 0° C. under vigorous stirring. After the complete conversion of M1 to P1 (or M2 to P2 for P2 homopolymer), for the block copolymer (BCP) formation, the second monomer (M2) was added ([M2]0=0.1 M) to the vial at 0° C. The reaction was quenched by excess ethyl vinyl ether (EVE) after the desired reaction time and precipitated in methanol at room temperature. The obtained purple solid was filtered and dried in vacuo. Those monomer conversions were calculated from the 1H NMR spectra of the remained crude mixture.
(2) Preparation of Blends of P150-b-P222 and P222
Each polymer (P150-b-P222 and P222) was dissolved in 0.5 g/L chloroform (more than 0.5 mL in 4 mL vial). Without aging, two solutions were mixed at room temperature with various P150-b-P222 and P222 with a ratio of 2:1 (or molar ratio of 1:2).
(3) Preparation of 2D Seeds from the Blend by Heating and Aging
The blended solutions were sealed with a Teflon lined cap and heated at 50° C. for 1 hour, followed by cooling down to 25° C. and aging for 3 days. The resulting 2D nanoparticles were observed by AFM and TEM imaging. In details, samples for TEM and AFM imaging were prepared by spin-coating one drop (ca. 0.05 mL) of the 2D seeds colloidal solution onto a carbon-coated copper grid (for TEM imaging) or freshly cleaved mica (for AFM imaging) (spinning rate=3000 rpm for 30 secs). Device-related information is described in the Supplementary Information.
(4) Preparation of 2D Rectangles with Tunable Length Via Living 2D CDSA of P2n Unimers
After diluting the 2D seeds solution to 0.03 g/L chloroform, a solution of lower molecular weight P2, (unimer, Mn=5.0-6.1 kDa, Ð<1.18) in 10 g/L chloroform was added to the solution of the 2D seeds with various unimer-to-seed (U/S) mass ratios. Then the samples were aged at X ° C. (variable temperatures).
(5) Growth Kinetic Studies of the Living 2D CDSA
To conduct growth kinetic studies of the 2D assembly in solution, we monitored the living 2D assembly over aging time after adding the unimer solution to the seed solution. For each nanostructure, length, width, height, area, aspect ratio, and angle distributions were estimated from the TEM and AFM images manually using the ImageJ software package which developed at the US National Institute of Health. For the statistical length analyses, more than 30 randomly picked objects were processed to determine the average values depending on the data set. Every particle in each image was counted to reduce subjectivity.
(1) Focus of this Study
The inventors previously reported that conjugated PCPV homopolymers containing fluorene and bulky substituents successfully underwent self-assembly because of their uniform orthorhombic crystalline arrays. For example, the semi-crystalline P222 [Mn=9.01 kDa (Ð=1.13)] homopolymer directly assembled into 2D rectangles in chloroform but any control of the structure was impossible because of its low solubility. The inventors then expanded this moiety to BCP microstructures composed of identical core-forming P222 blocks and solubilizing P150 shell blocks [P150-b-P222, Mn=38.6 kDa (Ð=1.10)]. This modification stabilized the P2 crystalline block, enabling precise control of widths and lengths via living CDSA, but a limitation was that only 1D nanofibers were prepared by this method. Based on these earlier investigations, the inventors attempted the formation of uniform 2D nanosheets by blending P222 and P150-b-P222 to achieve controlled co-assembly. Partially introduced P1 shell blocks in the blends should stabilize the main crystal array of the P222 homopolymer, overcoming the solubility issue of 2D nanorectangles in solution. To achieve this co-assembly, the inventors used a simple heating and aging method using the blends in chloroform and screened various conditions by changing the mass ratios of the two polymers, concentration, and temperature.
(2) Preparation of Uniform Monolayer Seed
After many optimizations, excellent co-assembly was achieved by heating a blend solution of P150-b-P222 and P222 at a ratio of 2:1 (or molar ratio of 1:2) in 0.5 g/L chloroform at 50° C. for 1 h. After cooling to 25° C. and aging for 3 days, transmission electron microscopy (TEM) imaging showed uniform mono-layers of 2D rectangles with an aspect ratio of 1.73 and an average angle of 92.9°, demonstrating excellent self-assembly via a self-seeding mechanism (
(3) The Tunable Area (Length) of 2D Nanosheet
With the uniform 2D seeds in hand, the inventors investigated the possibility of CDSA via seeded growth to further control the area of 2D nanosheets. A solution of lower molecular weight P210 (unimer, Mn=5.0 kDa, Ð=1.15) in 10 g/L chloroform was added to a solution of the 2D seeds in 0.03 g/L chloroform (An of 0.32 (±0.059) μm2) with various unimer-to-seed (U/S) mass ratios from 2 to 15. After optimizations, P210 successfully underwent CDSA to form uniform 2D rectangles, whose area increased linearly from 1.2 to 7.1 μm2 (Ð<1.02) according to U/S ratios after 3 weeks of aging at −13° C. (
(3) Kinetic Studies on 2D CDSA
Most notably, this uniaxial-living 2D CDSA is an excellent system for conducting kinetic studies of 2D assembly in solution. By real-time monitoring using TEM analysis, the inventors conducted growth kinetics by adding P210 homopolymer with various U/S ratios under the aforementioned conditions (0.03 g/L seeds in chloroform solutions at −13° C.), and measuring increases in length, as described in
To explore the effect of temperature on CDSA, the inventors again measured the rates at four different temperatures: 0, −10, −20, and −25° C. After first-order fitting, the initial rate constant k′ was found to increase from 3.0×10−3 to 1.1×10−2 as the temperature decreased from 0 to −25° C. These values allowed us to generate an Eyring plot to determine the activation enthalpy and entropy for the seeded-growth process, and they were negative values of −31.7 kJ/mol and −384 J/K-mol, respectively, indicating faster growth at lower temperatures (Table 2, Entries 6-9,
(4) Preparation of Multi-Block Comicelle with Adjusted Length and Height
Intriguingly, the uniaxial-living 2D CDSA could prepare more complex multi-block comicelles (BCM) via a series of seeded growth from various P2 unimers. Analogous to block copolymerization via living polymerization, the sequential addition of P210 and P215 unimers provided length and height controlled penta-BCMs along the (010) direction (unimers in 10 g/L chloroform, U/S ratio of 3, [2D seeds]=0.03 g/L in chloroform,
Since these precisely controlled 2D rectangles were composed of fluorescent conjugated PCPVs, they were visible under super-resolution structured illumination microscopy (SR-SIM) without additional dye. Interestingly, 2D seeds in the middle showed much higher fluorescence than the rest of the 2D sheets freshly formed from P2 unimers, indicating that the longer P2 emits stronger light. In addition, a video of the micelle solution recorded by confocal laser scanning microscopy (CLSM) shows a persistent shape and fluorescence stability without decomposition and photobleaching.
(5) Preparation of 2D Nanosheet with Adjusted Width and Length
The inventors have extended this study from the successful preparation of the length-tunable 2D nanosheet to the preparation of the width-tunable 2D nanosheet. In particular, when THF or chloroform was added as a co-solvent in a simple heating and aging method of dichloromethane solution of an example among PCPV homopolymer including fluorene and bulky substituents in the previous study, it was observed that the aspect ratio of nanosheet was tunable according to 18 different content ratios. The crystallinity of the 2D nanosheet was analyzed from film X-ray diffraction patterns and electron diffraction patterns using high-resolution TEM, the linear dependence of the aspect ratio of the nanosheets on the ration of co-solvent was inferred due to the difference between the surface energy of each plane and the crystal growth rate.
Accordingly, the inventors used method of adding the co-solvent and aging method after simple heating based on the linear dependence of the co-solvent effect in order to achieve preparation of 2D nanosheet in which the width and length were simultaneously adjusted using the blend. Specifically, various conditions were screened by changing the ratio and the concentration of the co-solvent from the method of preparing the uniform monolayer 2D seed.
As shown in
(6) Preparation of 2D Nanostructure with Adjusted Height According to Self-Assembly Selectively Grown in a Height Direction from 2D Seed with Adjusted Width
The inventors provided an environment in which the width and length of the 2D nanosheet, of which length is additionally adjusted using the obtained width-adjusted uniform 2D seed, are simultaneously adjusted via CDSA through seeded-growth. The 2D seeds of which widths were adjusted according to the volume ratio (0%, 10%, 20%, and 30%) of the co-solvent DCM at the time of seed formation (“SMC”) were used. Then, according to U/S ratio was adjusted, the 2D nanosheet whose length is adjusted by selectively growing in the (010) direction was prepared. In addition, in order to increase the rate of the length adjustment, the inventors added co-solvent DCM during CDSA process (“CMC”) through seeded-growth to adjust the length of the nanosheet. In this case, the volume % of DCM was set to 50%. In the conditions of each experiment, conditions other than the volume ratio of SMC and U/S ratio were set the same:
1) the concentration of the 2D seed: 0.2 g/L (in chloroform)
2) the molecular weight (Mw): 6.05 kDa
3) CMC %: 50%
4) aging temperature and time: 25° C. and 1-3 days
Interestingly, uniaxial living 2D CDSA occurred regardless of CMC 50%, and the length increased linearly according to U/S ratio. First, the length adjustment of the 2D seed of SMC 0% having 970 nm of the width succeeded from 1,890 nm to 4,160 nm (
As a result, 7 types of the 2D seed structures can be formed depending on the SMC %, the width of the 2D nanosheet was tunable from 970 nm to 230 nm in the (100) direction, and the length of the 2D nanosheet was tunable from 570 nm to 3,220 nm in the (010) direction. In addition, under adjusting the U/S ratio, it was possible to adjust the average length of the 2D nanosheet from 2 μm to 8 μm based on the 2D seed of which width was from 970 nm to 510 nm via 2D CDSA process.
In conclusion, the inventors successfully demonstrated the formation of uniform semi-conducting 2D rectangles having sharp edges from a semi-crystalline conjugated homopolymer by the uniaxial seeded-growth approach. This intriguing direction-selective assembly allowed us to control the length of 2D rectangles for the first time with narrow dispersity through 2D CDSA. Taking advantage of this uniaxial growth from a homopolymer, 2D growth kinetic studies revealed that the homopolymer self-assembly followed ideal first-order kinetics, similar to living polymerization. This result indicates that the polymer self-assembly follows ideal crystallization because disturbing elements, such as the conformational effect of a shell block or back-bone chain-folding, were eliminated. Lastly, 2D CDSA produced several complex but well-controlled penta-BCMs using various sizes of P2. Ultimately, we succeeded in a one-shot BCM formation based on an understanding of the growth kinetics, which provided an excellent guideline for optimizing self-assembly conditions. These precisely controlled uniform fluorescent 2D nanostructures would have great potential for optoelectronic applications.
The above description of the example embodiments is provided for the purpose of illustration, and it would be understood by those skilled in the art that various changes and modifications may be made without changing technical conception and essential features of the example embodiments. Thus, it is clear that the above-described example embodiments are illustrative in all aspects and do not limit the present disclosure. For example, each component described to be distributed can be implemented in a combined manner.
The scope of the inventive concept is defined by the following claims and their equivalents rather than by the detailed description of the example embodiments. It shall be understood that all modifications and embodiments conceived from the meaning and scope of the claims and their equivalents are included in the scope of the inventive concept.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2020-0046153 | Apr 2020 | KR | national |
| 10-2021-0046882 | Apr 2021 | KR | national |
| Entry |
|---|
| Yang et al. Journal of the American Chemical Society, J. Am. Chem. Soc. 2017, 139, 3082-3088 (Year: 2017). |
| Choi et al. Journal of the American Chemical Society, J. Am. Chem. Soc. 2018, 140, 17218-17225 (Year: 2018). |
| Song et al. Int. J. Mol. Sci. 2019, 20, 5166 (Year: 2019). |
| Sanghee Yang, “Formation of uniform one-dimensional- and two-dimensional-nanostructures from fluorescent semiconducting polymers with orthorhombic crystalline orientation”, General meeting, Koreanchemical society, Apr. 18-19, 2019, Suwon, Korea, 23 pages. |
| Sanghee Yang, Tae-Lim Choi, “Formation of uniform one-dimensional- and two-dimensional-nanostructures from fluorescent semiconducting polymers with orthorhombic crystalline orientation”, Sixth International Symposium Frontiers in Polymer Science, Frontiers in polymer science, May 5-8, 2019, Budapest, Hungary, 2 pages. |
| Number | Date | Country | |
|---|---|---|---|
| 20210324190 A1 | Oct 2021 | US |
