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C: Physical Processes in Nanomaterials and Nanostructures

Patterning the Internal Structure of Single Crystals by Gel Incorporation Xinyi Jin, Liao Chen, Yujing Liu, Tao Ye, Chong Hu, Jie Ren, Hongzheng Chen, and Hanying Li J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.9b02329 • Publication Date (Web): 02 May 2019 Downloaded from http://pubs.acs.org on May 2, 2019

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The Journal of Physical Chemistry

Patterning the Internal Structure of Single Crystals by Gel Incorporation Xinyi Jin, ‡ Liao Chen, ‡ Yujing Liu, Tao Ye, Chong Hu, Jie Ren, Hongzheng Chen, Hanying Li* MOE Key Laboratory of Macromolecular Synthesis and Functionalization, State Key Laboratory of Silicon Materials, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou, 310027, P. R. China

ABSTRACT: Single crystals are usually homogeneous, while heterogeneous internal structures can be constructed by incorporation of foreign materials. The existence of the homogeneous and heterogeneous states (termed as state “0” and “1”) inspires the idea to transform crystals between them so that the internal structures in the crystals become patternable. Here, gel-grown potassium dihydrogen phosphate single crystals transforming between the “0” and “1” states (without and with gel incorporation) are demonstrated by oscillating the crystallization conditions of growth rates (slow for “0”; fast for “1”) or growth media (solution for “0”; gel for “1”). As a result, crystals in the sequences of “010”, “001”, “011”, “100”, “110”, and “101” have been obtained. By showing the patterned structure through gel incorporation, this work presents one more degree of freedom for structural modification of crystals.

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INTRODUCTION Single crystals are widely known as homogeneous solids with uniform chemical compositions. On the other hand, heterogeneous structures, however, can be realized in synthetic single crystals by incorporating various “impurities”1,2 (e.g., gel-networks,3,4 particles,5-16 fibers,17,18 and possibly molecules19-23) into crystalline matrix, exhibiting similar composite structures as found in a variety of biogenic crystals.24 Intuitively, the internal structure of a crystal may become patternable with patterned distribution of the states (i.e., that of the “impurities”). This kind of patternability relies on two necessary conditions: 1) coexistence of both states at different areas inside an individual crystal with single-crystalline molecular packing mode (Figure 1a) as well as 2) a mechanism by which the two states of “0” and “1” can be transformed back and forth (Figure 1b). The first condition has been occasionally satisfied in synthetic crystals, while the second one is less frequently considered.

Figure 1. Schematic representations of the two necessary conditions to realize patterned structure of a crystal. (a) Condition 1: coexistence of state “0” (homogeneous structure packed by molecule


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“M”) and state “1” (heterogeneous structure with impurities) within an individual crystal is required. (b) Condition 2: These two states, “0” and “1”, can be transformed back and forth by a certain mechanism. Typically, a single crystal exhibits either “0” or “1” state. But the coexistence of both states within a crystal was found in limited cases. Calcite,3 calcium tartrate tetrahydrate25 and potassium dihydrogen phosphate (KDP) crystals26 forming at the interfaces of gels and solutions were reported to incorporate gel-networks in one side of the crystals while not in the other. And, the coexistence of both structures does not break the single-crystalline nature of the crystals.25,26 In addition to the gel-incorporation, it was reported that occlusion of certain dye would result in selective facet recognition and lead to inter-sector zoning of unevenly dyed KDP27 and potassium acid phthalate28 crystals. Highly relevantly, copolymer worms and vesicles have been recently introduced into calcite crystals at different regions.29 Similarly, intricate structure of gold single crystal composed of inner dense core and outer nanoporous shell was obtained.30 In addition to the condition 1, enabling the patterning still requires the condition 2 to transform a crystal between states. Intuitively, transforming the crystallization media containing different impurities might result in an alternate fashion. Recently, 3D DNA crystals have been assembled into layers in the presence or in the absence of conjugated guest molecules,31 We envision that these crystals may be suitable for this kind of structural patterning because the previous studies3243

on gel-incorporation mechanism have indicated that whether or not a growing crystal

incorporates surrounding gel-networks can be determined by crystallization conditions including growth rate and gel strength. In principle, oscillating these crystallization conditions may result in transforming the obtained crystals between the states without (i.e., “0”) and with (i.e., “1”) gelincorporation.



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In this work, we examine the crystallization of KDP in both silica and agarose gels. By changing the crystallization conditions between the slow and fast growth rates, the obtained crystals are regulated into the “0” and “1” states alternatively. Similar results are obtained by oscillating the crystallization media between solution and gel. Consequently, KDP single crystals with internal structural sequences such as “01010” are achieved. As such, patterning the internal structure of a crystal through gel incorporation is demonstrated. The widely-adopted gel-grown method and the successful growing control of the patterned KDP single crystals demonstrate a platform for fabricating various combinations of single crystals with gels and nanomaterials in a patterned manner.

RESULTS AND DISCUSSION

Figure 2. Optical microscope (OM) images of solution- and gel-grown KDP crystals. (a) A solution-grown crystal. b-d) Dissolution process of a crystal grown from a silica gel (4.5 w/v %) with an initial KDP concentration of 15 w/v%: (b) before dissolution, (c) during dissolution, (d) after dissolution in water. Insoluble gel residues and bubbles emerge near the dissolving crystal,


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as shown in (c) and (d). In (a) and (b), the two tips of the KDP crystals exhibit the shape of pyramid, as schemed in Figure 3c. And the tips appear dark because of the reflection of light in the OM. The internal structures of single crystals were first patterned by oscillating crystallization rates. We examined the KDP crystals grown from silica gels by diffusing a non-solvent, methanol, into the gelled KDP solution. In contrast to the typical solution-grown transparent crystals (Figure 2a), gel-grown KDP crystals incorporate the silica gel-networks and become opaque, as previously reported.26 Similarly, we obtained the opaque crystals (Figure 2b). As the opaque crystal was gradually dissolved, a block of gel that resembled the shape of the original crystal remained (Figure 2b-d), indicative of the uniform incorporation of the gel-networks inside the obtained crystals (state “1”). Interestingly, extending the crystallization in gels resulted in a two-layer structure, with an additional shell layer of transparent crystal on the opaque core (Figure 3a, c). The transparency of the shell suggested that it was a layer of gel-free crystal similar to the solution-grown crystals, which was evidenced by elemental mapping. The crystal was cut across the opaque core and transparent shell to expose a cross-section. After gently etching, the cross-section was examined by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) (Figure 3b). Both SEM image and EDX mappings clearly revealed the boundary between the core and the shell: there was potassium all over the cross-section, while, in sharp contrast, silicon element from gel-networks mainly concentrated in the core area. The same section was further dissolved in water and the results were consistent with the SEM and EDX data: there was no insoluble residue remained until the core began to be dissolved and then with the slow dissolution of the opaque core, a block of insoluble substance similar to the shape of the original core was ultimately left behind (Figure 3d). Therefore, extended crystallization led to a transition from gel-incorporated



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core to the gel-free shell. Surprisingly, this transition did not induce the change in crystallographic structure.

Figure 3. Two-layer “10” structure of KDP single crystals grown from a silica gel (9 w/v %) with an initial KDP concentration of 10 w/v%. (a) An OM image and (c) a schematic representation of the crystal with an opaque core (state “1” with incorporated gel-networks) and a transparent shell (state “0” without gel-networks). (b) A clear boundary between the “0” and “1” states can be seen from both SEM imaging and EDX mappings of K and Si elements for a transverse section of a cuboid cut from the crystal in (a) after gentle etching. (d) OM images of the same cuboid slice in (b) before, during and after (from left to right) dissolution in water. (e) A SAED pattern of an area


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containing the boundary between the “0” and “1” states. (f, g) Laue diffraction patterns for the crystal with a two-layer structure of “10” along the [100] and [001] directions, respectively. The indexed patterns are shown in Figure S3. The “streaking” of the spots was due to the finite thickness of the detector chamber. Powder X-ray diffraction (PXRD) patterns (Figure S1) proved that the crystals were of tetragonal KDP phase and showed no diffraction peaks shift or split in all three crystal states: “0”, “10” and “101”. Selected-area electron diffraction (SAED) pattern (Figure 3e) of an area containing boundary between the core and the shell showed a single set of diffraction spots, together with clear and definite micro-beam (0.5 mm) Laue diffraction patterns along the [100] and [001] directions (Figure 3f, g), further demonstrated that the two-layer crystals maintained single-crystallinity in both micro- and macro-scales. Consistently with the single-crystallinity, the crystals illuminated and extinguished simultaneously when rotated under cross-polarized light (Figure S2). Based upon the above evidences, we conclude that the KDP single crystals grown from the silica gels can be patterned into a “10” fashion. Next, we demonstrate that further patterning is possible because crystallization of the “10” crystals can be transformed back to the “state 1” to exhibit a “101” sequence. After obtained the “10” two-layer crystals, non-solvent was added again to increase its concentration and to induce the supersaturation of KDP. As a result, a third layer of crystal formed and turned the crystals into opaque (Figure 4a, c). Similarly, a crystal was cut through the three layers to expose the section with “opaque-transparent-opaque” sequence (Figure 4b). The structure of the section was examined by monitoring its dissolution process (Figure 4b, d). As the section started to dissolve, insoluble gel-networks were exposed. However, after the dissolution front reached the middle transparent layer, hardly any residue was left. Once the middle transparent layer totally



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disappeared, the opaque core began to dissolve and insoluble gel-networks appeared again. Therefore, the three-layer KDP crystals were patterned into a “101” fashion.

Figure 4. Dissolution process of a three-layer KDP single crystal “101” grown from a silica gel (4.5 w/v%) with an initial KDP concentration of 5 w/v %. (a, c) An OM image and a schematic representation of the crystal. (b) OM images of a transverse section of a cuboid cut from the crystal: (left) before dissolution, (middle) during dissolution and (right) after complete dissolution. The gel residues emerged only in the first and the third layers, with the residue of the first layer floating away because of its light weight. (d) A schematic representation of the dissolution process. The achievement of the “101” crystals proves that the crystal can be transformed back and forth between the state “1” and “0” to pattern its internal structure. The mechanism for the transforming is attributed to the previously-reported speed-dependent gel incorporation:32,33 crystallization speeds faster than a critical value34-36 lead to crystals with gel-networks incorporated (state “1”), while crystals under slower growth rates tend to push away gel-networks and result in comparatively pure solids (state “0”). During the crystallization of the “101” crystals, the growth rate oscillated in a “fast-slow-fast” sequence to induce the transforming between “state 1” and “0”.


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At the initial stage, diffusion of the non-solvent led to a high level of supersaturation and relatively high crystallization rate, resulting in gel incorporation and “state 1”. Subsequent crystallization reduced gradually the concentration of the KDP solution and, thus, the growth rate. Once the rate reached the critical value for gel incorporation, the slow growing crystallization front turned into gel-free solid (i.e., “state 0”). Finally, the addition of the second non-solvent raised the supersaturation level and the growth rate. Accordingly, the fast-approaching crystallization front started to incorporate gel-networks again, resulting in “state 1”. This critical growth rate for gel incorporation is not easily measured because the rate changes continuously. However, the effect of the critical growth rate can be observed. Crystals were grown with 5 w/v %, 10 w/v %, 15 w/v% and 20 w/v % of the initial KDP concentrations (C0) and in all the four situations, two-layer “10” KDP crystals were obtained. The extent of gel-networks incorporation inside the whole crystal including both the “0” and “1” parts was analyzed by measuring the size ratio of the opaque region (state “1”) to the whole crystal (state ‘1” plus state “0”). And the size ratio is defined in Figure S4. Two features were clearly seen (Figure S4). First, for each of the four situations, forty crystals from different vials were measured and the size ratio was very consistent with a standard deviation below 20%, indicating the existence of the critical growth rate. Second, the value of the size ratio increased with the increase of KDP concentration, indicating that higher C0 led to more incorporated gel networks. These two features are consistent with the mechanism of the speed-dependent gel incorporation.32,33 In addition to the crystallization rate, crystallization media were alternated between solutions and gels to examine the feasibility of patterning. For this purpose, the crystals need to be put into and removed from gel media. And a gel formed and deformed rapidly enough is needed as the crystals will be damaged (e.g., etched or dissolved) otherwise. And a physically bonded gel formed



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by agarose (type IX, Sigma) that gels within 5 minutes in cold water bath, was selected instead of the chemically bonded silica gel that forms in 1-3 days. The feasibility of patterning was then investigated in 3 steps. First, whether the KDP crystals incorporate the gel networks was investigated as they were grown from the agarose gels. The obtained KDP crystals grown from agarose gels were opaque, indicative of gel incorporation. Further dissolution of the crystals exposed the incorporated gel networks (Figure S5). Therefore, crystals with state “1” can be achieved from the agarose gel media. Second, the gel-grown KDP crystals were used as seeds to overgrow the KDP crystal in either “0” or “1” state. On one hand, the method of temperature-drop in a saturated KDP solution (termed as “condition 0”) was adopted to grow the crystal into state “0”. Both OM and SEM images clearly showed an “opaque-transparent” two-layer structure, indicating the overgrowth of a transparent crystal on the opaque seed (Figure S6). Imaging a transverse section of the crystal (Figure S6c-e) as well as gradual dissolution of the crystal (Figure S7) further confirmed the structural difference between the two layers: with and without the gel incorporation. More importantly, as shown in Figure 5a-d, thickness of the overgrown layer could be well regulated by the crystallization time. On the other hand, diffusion of dimethyl sulfoxide, as a non-solvent, into an agarose gel containing KDP solution (termed as “condition 1”) was adopted to obtain gel-grown crystals with state “1”. Similarly, overgrown opaque crystals were obtained with regulated thicknesses (Figure 5e-h).


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Figure 5. Crystallization from a seed crystal to achieve overgrown layers with varied thicknesses. (a-d) A series of OM images recording the overgrowth in a saturated KDP solution for (a, b) 0 minutes, (c) 5 minutes, and (d) 15 minutes, showing the gradually increased thickness of the overgrown layer in the state “0”. (e-h) A series of OM images recording the overgrowth in an agarose gel for (e, f) 0 minutes, (g) 180 minutes, and (h) 2 days, showing the gradually increased thickness of the overgrown layer in the state “1”. Slower mass transport velocity in the gel media leaded to extended growth time to reach the identical layer thickness achieved in solution. Finally, the crystals were transformed between the state “0” and “1” back and forth by refreshing their growth conditions with either condition “0” or condition “1” correspondingly. In order to sharply contrast the state “0” with “1”, we dyed1,44 the gel-grown crystals in state “1” with a purple dye called crystal violet by introducing the dye into the gel media. Consequently, the crystals in their state “1” were evenly colored purple (Figure S8) in contrast with the transparent solutiongrown crystals in state “0”. Next, crystallization from a seed in varied sequences of growth conditions resulted in two new crystal layers with various structures of “01”, “00”, “11”, and “10” (Figure 6a). Further, three-layer structures were obtained with the sequences of “011”, “010”, “001”, “110”, “101”, “100” (Figure 6a). In principle, structures with arbitrary binary sequences



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can be designed. As an example, a more complex structure of “01010” was demonstrated (Figure 6b). Symmetric and well-defined Laue diffraction spots along two crystallographic directions of the crystal proved its single-crystallinity (Figure 6c, d). Therefore, we conclude that patterning the internal structures of the crystal by alternating crystallization media between solutions and gels is feasible.

Figure 6. Patterning KDP single crystals into a series of sequences by alternating crystallization media. (a) OM images of the obtained crystals. The purple color of the gel-incorporated (state “1”)


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layer is from a dye (crystal violet) that was added in gel to dye the gel-grown crystal so that sharp contrast between the “0” and “1” layer can be clearly seen. (b) An OM image of a crystal with five-layer structure “01010”. (c, d) Laue diffraction patterns of the crystal “01010” along the [100] and [001] directions. The indexed patterns are shown in Figure S3. Similar patterned crystals have been found in Nature. In molluscan shells, organic components are not uniformly distributed within the minerals. 24,45-48 During biomineralization, crystals and foreign materials are assembled into a patterned fashion.23-25 The calcitic prismatic layer presents an alternated pattern formed by micro-sized periodical zonations of magnesium, sulfur and organic components with variable concentrations. The patterning mechanism has been suggested to be associated with the regular rhythm of biomineralization and/or periodic temperature changes such as seasonal, semi-diurnal or diurnal patterns.47,48 These microgrowth lines with regions composed of dense mineral and organic zones are similar with the patterned structures of the single crystals achieved in this work. And the oscillating crystallization method is analogous to the process of periodic biomineralization conditions. Thus, these synthetic patterned single crystals should have implications for understanding the formation of the patterned biominerals. Patterning the internal structure of a single crystal enables the patterning of its properties that are modulated by the patterned gel incorporation. More importantly, the foreign materials incorporated into crystal host are not limited to the gel networks. Nanomaterials dispersed in gel media can be incorporated together with the gel network.18,39-42 Consequently, patterned incorporation of a variety of functional nanomaterials can be realized to pattern the crystal properties in a wide range. As an example shown in Figure S9, we prepared KDP crystals with “10” structure in the silica gels containing gold nanoparticles which were merely restrained in the wine-red crystal state “1” core area where gel-network was occluded.



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CONCLUSIONS In summary, we have demonstrated that crystallization in gel media can be used to pattern the internal structure of single crystals. By oscillating the crystallization conditions of growth rate between the slow and fast modes, the gel-grown KDP crystals have exhibited a patterned internal structure combining regions without and with incorporated gel networks. Similarly, oscillating the crystallization media between solutions and gels has led to patterned structures. Interestingly, the crystal maintains the structural integrity and diffracts electron beam and X-ray as single crystal. Our work provides a platform to study the formation mechanisms of the patterned crystals found in nature. This work also suggests an approach for modifying the structure and, thus, the properties of crystals in a patterned fashion.

ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website. Experimental section, PXRD patterns, OM and SEM images. AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] Author Contributions ‡These authors contributed equally to this work.


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Notes The authors declare no competing financial interest. ACKNOWLEDGMENT This work was supported by the 973 Program (2014CB643503), National Natural Science Foundation of China (51625304, 51461165301, 51873182). We thank Multiwire Laboratories, Ltd for the Laue measurement. REFERENCES 1. Shtukenberg, A. G.; Ward, M. D.; Kahr, B. Crystal growth with macromolecular additives. Chem. Rev. 2017, 117, 14042-14090. 2. Weber, E.; Pokroy, B. Intracrystalline inclusions within single crystalline hosts: from biomineralization to bio-inspired crystal growth. CrystEngComm. 2015, 17, 5873–5883. 3. Nickl, H. J.; Henisch, H. K. J. Growth of calcite crystals in gels. Electrochem. Soc. 1969, 116, 1258-1260. 4. Li, H. Y.; Xin, H. L.; Muller, D. A.; Estroff, L. A. Visualizing the 3D internal structure of calcite single crystals grown in agarose hydrogels. Science. 2009, 326, 1244-1247. 5. Li, C.; Qi, L. M. Bioinspired fabrication of 3D ordered macroporous single crystals of calcite from a transient amorphous phase. Angew. Chem. Int. Ed. 2008, 47, 2388-2393. 6. Sindoro, M.; Feng, Y.; Xing, S.; Li, H.; Xu, J.; Hu, H.; Liu, C.; Wang, Y.; Zhang, H.; Shen, Z.; et al. Triple-layer (au@perylene)@ polyaniline nanocomposite: unconventional growth of



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