Substrate-assisted Growth Research Articles

2D Perovsktie Substrate-Assisted CsPbI3 Film Growth for High-Efficiency Solar Cells.

High-quality perovskite films are beneficial for fabricating perovskite solar cells (PSCs) with excellent photoelectric performance. The substrate on which the perovskite film grows plays a profound role in improving the crystallization quality of the perovskite film. Here, we proposed a novel method for optimizing CsPbI3 perovskite films, that is, two-dimensional (2D) perovskite substrate-assisted growth (2D-PSAG) method. The prepared PEA2PbI4 2D perovskite with proper wettability and roughness is used as a substrate to fabricate the high-quality CsPbI3 film. Moreover, it is found that PEA cations show a vertical gradient distribution within the whole CsPbI3 film because of their bottom-up self-diffusion. Also, PEA cations induce the moderate distortion of [PbI6]4- octahedron and slight lattice contraction of CsPbI3 by chemically bonding between Pb and N atoms. Surprisingly, the trace amounts of PEA cations lead to a bottom-up gradient phase transition from γ-CsPbI3 to β-CsPbI3. Therefore, the energy-level alignment becomes more matched at the interface of the perovskite layer/hole transport layer (poly3-hexylthiophene, P3HT), which denotes a large improvement of hole transport and extraction in PSCs made with the 2D-PSAG method. As a result, the CsPbI3-based PSCs with P3HT as a hole transport layer exhibit a champion efficiency of 17.13%, while the control device exhibits a PCE of only 14.16%. The PSCs made by the 2D-PSAG method retain above 70% of the initial PCE value after storage of 9 days in air (RH 10-20%), while the control device decomposes completely after 9 days. The improved stability could originate from the steric effects of PEA cations and the high crystallization quality of the mixed-phase CsPbI3 film. Therefore, 2D-PSAG is a novel and promising strategy to develop all-inorganic PSCs with high performance and stability.

Binder-free electrodes for advanced potassium-ion batteries: A review

Potassium-ion batteries (PIBs) have attracted enormous attention due to the abundance of potassium resources, low cost, fast ionic conductivity of electrolyte and relatively high operating voltage. Despite great efforts and progress, researches on PIBs are still at the initial stage, especially in the emerging field of flexible and wearable PIBs. The inevitable challenges for PIBs include low reversible capacity, unsatisfactory cycling stability and insufficient energy density, the solution to which mostly relies on designing advanced electrodes. Binder-free electrodes have emerged as promising electrode architecture for PIBs. Such electrodes avoid the use of insulating binders, which can be designed with various synergistic functional materials to address the aforementioned PIB issues and be endowed with flexibility/wearability. In this review, we mainly summarize the recent progress on binder-free electrodes for PIBs, with the focus on the methodologies, detailed strategies and functional materials for electrode construction. One strategy for binder-free electrodes is to assemble free-standing architecture with the help of carbon nanotubes (CNTs), graphitic fibers, and other carbon or mechanically robust materials, either alone or in combination. The other effective strategy is current collector substrate-assisted direct growth, including the use of carbon cloth, metal, MXenes and other conductive substrates. Additionally, challenges and research opportunities are put forward at the end as the guidance for future development of binder-free PIB devices.

High-performance Ni-V-Fe metal-organic framework electrocatalyst composed of integrated nanowires and nanosheets for oxygen evolution reaction

Rational design of nanostructured metal-organic frameworks (MOFs) for catalytic applications is an ongoing challenge. Here, a new hierarchical NiVFe-MOF composed of self-supported nanowires and nanosheets are first prepared through substrate-assisted solvothermal growth. The MOF nanowires and nanosheets are tightly assembled into an integrated nanostructure with facile mass transfer. At the same time, the microstructure of the nanowires/nanosheets exhibits abundant active sites due to the hierarchical porosity. As resultant NiVFe-MOF exhibits significantly enhanced activity in oxygen evolution reaction (OER). The resulting MOF yields a low overpotential (225 mV, 10 mA cm−2; 269 mV, 100 mA cm−2) and high stability after long-term cycling test, suggesting a state-of-the-art performance. This study can provide new insights on rational design and synthesis of nanostructured MOFs for catalytic applications.

Band gap, dielectric constant, and susceptibility of DNA layers as controlled by vanadium ion concentration

Deoxyribonucleic acid (DNA) doped with transition metal ions shows great versatility for molecular-based biosensors and bioelectronics. Methodologies for developing DNA lattices (formed by synthetic double-crossover tiles) and DNA layers (used by natural salmon) doped with vanadium ions (V3+), as well as an understanding of the physical characteristics of V3+-doped DNA nanostructures, are essential in practical applications in interdisciplinary research fields. Here, DNA lattices and layers doped with V3+ are constructed through substrate-assisted growth and drop-casting methods. In addition, enhanced physical characteristics such as the band gap energy, work function, dielectric constant, and susceptibility of V3+-doped DNA nanostructures with varying V3+ concentration ([V3+]) are investigated. The critical concentration ([V3+]C) at a given amount of DNA was predicted based on an analysis of the phase transition of DNA lattices from crystalline to amorphous with specific [V3+]. Generally, the [V3+]C provided crucial information on the structural stability and extremum physical characteristics of V3+-doped DNA nanostructures due to the optimum incorporation of V3+ into DNA. We obtained the optical absorption spectra for energy band gap estimation; Raman spectra for identifying the preferential coordination sites of V3+ in DNA; x-ray photoelectron spectra to examine the chemical state, chemical composition, and functional groups; and ultraviolet photoelectron spectra to estimate the work function. In addition, we addressed the electrical properties (i.e. current, capacitance, dielectric constant, and storage energy) and magnetic properties (magnetic field-dependent and temperature-dependent magnetizations and susceptibility) of DNA layers in the presence of V3+. The development of biocompatible materials with specific optical, electrical, and magnetic properties is required for future applications because they must have designated functionality, high efficiency, and affordability.

Gold Aerogel Monoliths with Tunable Ultralow Densities.

Herein we report the fabrication of ultralight gold aerogel monoliths with tunable densities and pore structures. Gold nanowires are prepared at the gram scale by substrate-assisted growth with uniform size, ultrathin diameters, high purity, and a high aspect ratio. Freeze-casting of suspensions of these nanowires produces free-standing, monolithic aerogels with tunable densities from 6 to 23 mg/cm3, which to the best of our knowledge represents the lowest density monolithic gold material. We also demonstrate that the pore geometries created during freeze-casting can be systematically tuned across multiple length scales by the selection of different solvents and excipients in the feedstock suspension. The mechanical behavior of porous materials depends on relative density and pore architectures.

Metal and Lanthanide Ion-Co-doped Synthetic and Salmon DNA Thin Films.

Researchers have begun to use DNA molecules as an efficient template for arrangement of multiple functionalized nanomaterials for specific target applications. In this research, we demonstrated a simple process to co-dope synthetic DNA nanostructures (by a substrate-assisted growth method) and natural salmon DNA thin films (by a drop-casting method) with divalent metal ions (M2+, e.g., Co2+ and Cu2+) and trivalent lanthanide ions (Ln3+, e.g., Tb3+ and Eu3+). To identify the relationship among the DNA and dopant ions, DNA nanostructures were constructed while varying the Ln3+ concentration ([Ln3+]) at a fixed [M2+] with ion combinations of Co2+–Tb3+, Co2+–Eu3+, Cu2+–Tb3+, and Cu2+–Eu3+. Accordingly, we were able to estimate the critical [Ln3+] (named the optimum [Ln3+], [Ln3+]O) at a given [M2+] in the DNA nanostructures that corresponds to the phase change of the DNA nanostructures from crystalline to amorphous. The phase of the DNA nanostructures stayed crystalline up to [Tb3+]O ≡ 0.4 mM and [Eu3+]O ≡ 0.4 mM for Co2+ ([Tb3+]O ≡ 0.6 mM and [Eu3+]O ≡ 0.6 mM for Cu2+) and then changed to amorphous above 0.4 mM (0.6 mM). Consequently, phase diagrams of the four combinations of dopant ion pairs were created by analyzing the DNA lattice phases at given [M2+] and [Ln3+]. Interestingly, we observed extrema values of the measured physical quantities of DNA thin films near [Ln3+]O, where the maximum current, photoluminescence peak intensity, and minimum absorbance were obtained. M2+- and Ln3+-multidoped DNA nanostructures and DNA thin films may be utilized in the development of useful optoelectronic devices or sensors because of enhancement and contribution of multiple functionalities provided by M2+ and Ln3+.

DNA nanostructures doped with lanthanide ions for highly sensitive UV photodetectors.

Deoxyribonucleic acid (DNA) and lanthanide ions (Ln3+) exhibit exceptional optical properties that are applicable to the development of nanoscale devices and sensors. Although DNA nanostructures and Ln3+ ions have been investigated for use in the current state of technology for more than a few decades, researchers have yet to develop DNA and Ln3+ based ultra-violet (UV) photodetectors. Here, we fabricate Ln3+ (such as holmium (Ho3+), praseodymium (Pr3+), and ytterbium (Yb3+))‒doped double crossover (DX)‒DNA lattices through substrate-assisted growth and salmon DNA (SDNA) thin films via a simple drop-casting method on oxygen (O2) plasma-treated substrates for high performance UV photodetectors. Topological (AFM), optical (UV-vis absorption and FTIR), spectroscopic (XPS), and electrical (I‒V and photovoltage) measurements of the DX‒DNA and SDNA thin films doped with various concentrations of Ln3+ ([Ln3+]) are explored. From the AFM analysis, the optimum concentrations of various Ln3+ ([Ln3+]O) are estimated (where the phase transition of Ln3+‒doped DX‒DNA lattices takes place from crystalline to amorphous) as 1.2 mM for Ho3+, 1.5 mM for Pr3+, and 1.5 mM for Yb3+. The binding modes and chemical states are evaluated through optical and spectroscopic analysis. From UV-vis absorption studies, we found that as the [Ln3+] was increased, the absorption intensity decreased up to [Ln3+]O, and increased above [Ln3+]O. The variation in FTIR peak intensities in the nucleobase and phosphate regions, and the changes in XPS peak intensities and peak positions detected in the N 1 s and P 2p core spectra of Ln3+‒doped SDNA thin films clearly indicate that the Ln3+ ions are properly bound between the bases (through chemical intercalation) and to the phosphate backbone (through electrostatic interactions) of the DNA molecules. Finally, the I‒V characteristics and time-dependent photovoltage of Ln3+‒doped SDNA thin films are measured both in the dark and under UV LED illuminations (λLED = 382 nm) at various illumination powers. The photocurrent and photovoltage of Ln3+‒doped SDNA thin films are enhanced up to the [Ln3+]O compared to pristine SDNA due to the charge carriers generated from both SDNA and Ln3+ ions upon the absorption of light. From our observations, the photovoltages as function of illumination power suggest higher responsivities, and the photovoltages as function of time are almost constant which indicates the stability and retention characteristics of the Ln3+‒doped SDNA thin films. Hence, our method which provides an efficient doping of Ln3+ into the SDNA with a simple fabrication process might be useful in the development of high-performance optoelectronic devices and sensors.

Streptavidin-Decorated Algorithmic DNA Lattices Constructed by Substrate-Assisted Growth Method.

The ultimate goal of DNA computing is to store information at higher density and solve complex problems with less computational time and minimal error. Most algorithmic DNA lattices have been constructed using the free-solution growth (FSG) annealing method, and hairpin-embedded DNA rule tiles have been introduced in most algorithmic implementations to differentiate 0- and 1-bit information. Here, we developed streptavidin (SA)-decorated algorithmic COPY (produced line-like patterns with biotinylated 1-bit rule tiles) and XOR (triangle-like patterns) lattices constructed by a substrate-assisted growth (SAG) method and FSG. SA decoration in algorithmic lattices provides an efficient platform for visualizing bit information, and the SAG method in algorithmic assembly offers full coverage of algorithmic lattices on a substrate with a relatively lower DNA concentration than previous methods. The algorithmic COPY and XOR lattices assembled with various ratios of 0- and 1-bit rule tiles were verified by atomic force microscopy. We found that even asymmetric DNA patterns produced by certain algorithmic logic gates could be easily constructed by SAG. Finally, we evaluated sorting factors and error rates of algorithmic COPY and XOR lattices to determine the bit population and quality of the algorithmic assembly. Because of the catalytic effect of the substrate, the sorting factor of algorithmic DX-DNA lattices did not greatly influence the specific rules (i.e., COPY and XOR logic gates) annealed by SAG. Additionally, we found that the overall error rates of algorithmic DX-DNA lattices prepared by the FSG and SAG methods were low, within the range of 1-3%. Hence, the self-assembled algorithmic patterns generated with DNA molecules may serve as a scaffold for molecular demultiplexing circuits and computing.

Synthesis and characterization of doxorubicin hydrochloride drug molecule-intercalated DNA nanostructures

In this paper, we demonstrate the feasibility of constructing DNA nanostructures (i.e. DNA rings and double-crossover (DX) DNA lattices) with appropriate doxorubicin hydrochloride (DOX) concentration and reveal significant characteristics for specific applications, especially in the fields of biophysics, biochemistry and medicine. DOX-intercalated DNA rings and DX DNA lattices are fabricated on a given substrate using the substrate-assisted growth method. For both DNA rings and DX DNA lattices, phase transitions from crystalline to amorphous, observed using atomic force microscopy (AFM) occurred above a certain concentration of DOX (at a critical concentration of DOX, 30 μM of [DOX]C) at a fixed DNA concentration. Additionally, the coverage percentage of DNA nanostructures on a given substrate is discussed in order to understand the crystal growth mechanism during the course of annealing. Lastly, we address the significance of optical absorption and photoluminescence characteristics for determining the appropriate DOX binding to DNA molecules and the energy transfer between DOX and DNA, respectively. Both measurements provide evidence of DOX doping and [DOX]C in DNA nanostructures.

Topological, chemical and electro-optical characteristics of riboflavin-doped artificial and natural DNA thin films.

DNA is considered as a useful building bio-material, and it serves as an efficient template to align functionalized nanomaterials. Riboflavin (RF)-doped synthetic double-crossover DNA (DX-DNA) lattices and natural salmon DNA (SDNA) thin films were constructed using substrate-assisted growth and drop-casting methods, respectively, and their topological, chemical and electro-optical characteristics were evaluated. The critical doping concentrations of RF ([RF]C, approx. 5 mM) at given concentrations of DX-DNA and SDNA were obtained by observing the phase transition (from crystalline to amorphous structures) of DX-DNA and precipitation of SDNA in solution above [RF]C. [RF]C are verified by analysing the atomic force microscopy images for DX-DNA and current, absorbance and photoluminescence (PL) for SDNA. We study the physical characteristics of RF-embedded SDNA thin films, using the Fourier transform infrared spectrum to understand the interaction between the RF and DNA molecules, current to evaluate the conductance, absorption to understand the RF binding to the DNA and PL to analyse the energy transfer between the RF and DNA. The current and UV absorption band of SDNA thin films decrease up to [RF]C followed by an increase above [RF]C. By contrast, the PL intensity illustrates the reverse trend, as compared to the current and UV absorption behaviour as a function of the varying [RF]. Owing to the intense PL characteristic of RF, the DNA lattices and thin films with RF might offer immense potential to develop efficient bio-sensors and useful bio-photonic devices.

Electromagnetic and optical characteristics of Nb5+-doped double-crossover and salmon DNA thin films

We report the fabrication and physical characteristics of niobium ion (Nb5+)-doped double-crossover DNA (DX-DNA) and salmon DNA (SDNA) thin films. Different concentrations of Nb5+ ([Nb5+]) are coordinated into the DNA molecules, and the thin films are fabricated via substrate-assisted growth (DX-DNA) and drop-casting (SDNA) on oxygen plasma treated substrates. We conducted atomic force microscopy to estimate the optimum concentration of Nb5+ ([Nb5+]O = 0.08 mM) in Nb5+-doped DX-DNA thin films, up to which the DX-DNA lattices maintain their structures without deformation. X-ray photoelectron spectroscopy (XPS) was performed to probe the chemical nature of the intercalated Nb5+ in the SDNA thin films. The change in peak intensities and the shift in binding energy were witnessed in XPS spectra to explicate the binding and charge transfer mechanisms between Nb5+ and SDNA molecules. UV-visible, Raman, and photoluminescence (PL) spectra were measured to determine the optical properties and thus investigate the binding modes, Nb5+ coordination sites in Nb5+-doped SDNA thin films, and energy transfer mechanisms, respectively. As [Nb5+] increases, the absorbance peak intensities monotonically increase until ∼[Nb5+]O and then decrease. However, from the Raman measurements, the peak intensities gradually decrease with an increase in [Nb5+] to reveal the binding mechanism and binding sites of metal ions in the SDNA molecules. From the PL, we observe the emission intensities to reduce them at up to ∼[Nb5+]O and then increase after that, expecting the energy transfer between the Nb5+ and SDNA molecules. The current–voltage measurement shows a significant increase in the current observed as [Nb5+] increases in the SDNA thin films when compared to that of pristine SDNA thin films. Finally, we investigate the temperature dependent magnetization in which the Nb5+-doped SDNA thin films reveal weak ferromagnetism due to the existence of tiny magnetic dipoles in the Nb5+-doped SDNA complex.

Structural stability and electrical characteristic of DNA lattices doped with lanthanide ions

The main aim of doping DNA lattices with lanthanide ions (Ln-DNA complex) is to change the physical functionalities for specific target applications such as electronics and biophotonics. Ln–DNA complexes based on a double-crossover DNA building block were fabricated on glass using a substrate-assisted growth method. We demonstrated the structural stability of Ln–DNA complexes as a function of Ln ion concentration by the atomic force microscopy. The Ln ion doping in DNA lattices was examined using a chemical reduction process, and the electrical characteristics of Ln–DNA complexes were tested using a semiconductor parameter analyzer. The structural phase transition of DNA lattices from the crystalline to amorphous phases occurred at a certain critical concentration of each Ln ion. Ln ions in DNA lattices are known to be intercalated between the base pairs and bound with phosphate backbones. When DNA lattices are properly doped with Ln ions, Ln–DNA complexes revealed the complete deformation with chemical reduction process by ascorbic acid. The current increased up to a critical Ln ion concentration and then decreased with further increasing Ln ions. Ln–DNA complexes will be useful in electronics and photonics because of their unique physical characteristics.

Hall transport of divalent metal ion modified DNA lattices

We investigate the Hall transport characteristics of double-crossover divalent metal ion (Cu2+, Ni2+, Zn2+, and Co2+)-modified DNA (M-DNA) lattices grown on silica via substrate-assisted growth. The electronic characteristics of the M-DNA lattices are investigated by varying the concentration of the metal ions and then conducting Hall measurements, including resistivity, Hall mobility, carrier concentration, and magneto resistance. The tendency of the resistivity and Hall mobility was to initially decrease as the ion concentration increased, until reaching the saturation concentration (Cs) of each metal ion, and then to increase as the ion concentration increased further. On the other hand, the carrier concentration revealed the opposite tendency as the resistivity and Hall mobility. The specific binding (≤Cs) and the nonspecific aggregates (>Cs) of the ions into the DNA lattices were significantly affected by the Hall characteristics. The numerical ranges of the Hall parameters revealed that the M-DNA lattices with metal ions had semiconductor-like characteristics. Consequently, the distinct characteristics of the electrical transport through M-DNA lattices will provide useful information on the practical use of such structures in physical devices and chemical sensors.

Construction and characterization of Cu2+, Ni2+, Zn2+, and Co2+ modified-DNA crystals

We studied the physical characteristics of modified-DNA (M-DNA) double crossover crystals fabricated via substrate-assisted growth with various concentrations of four different divalent metallic ions, Cu2+, Ni2+, Zn2+, and Co2+. Atomic force microscopy (AFM) was used to test the stability of the M-DNA crystals with different metal ion concentrations. The AFM images show that M-DNA crystals formed without deformation at up to the critical concentrations of 6 mM of [Cu2+], 1.5 mM of [Ni2+], 1 mM of [Zn2+], and 1 mM of [Co2+]. Above these critical concentrations, the M-DNA crystals exhibited deformed, amorphous structures. Raman spectroscopy was then used to identify the preference of the metal ion coordinate sites. The intensities of the Raman bands gradually decreased as the concentration of the metal ions increased, and when the metal ion concentrations increased beyond the critical values, the Raman band of the amorphous M-DNA was significantly suppressed. The metal ions had a preferential binding order in the DNA molecules with G–C and A–T base pairs followed by the phosphate backbone. A two-probe station was used to measure the electrical current–voltage properties of the crystals which indicated that the maximum currents of the M-DNA complexes could be achieved at around the critical concentration of each ion. We expect that the functionalized ion-doped M-DNA crystals will allow for efficient devices and sensors to be fabricated in the near future.

Streptavidin bound DNA open tube and Zn2+-doped DNA open lattice

DNA is one of the most promising molecules for use in nanotechnology because it has a nanoscale size and also has the ability for self-assembly. In this paper, we discuss the use of free-solution growth for a 1D DNA open tube (OT) and substrate-assisted growth for a 2D open lattice (OL), which can both achieve similar design schemes. We introduced biotinylated OT and OL, which can be bound with streptavidin for visualization, to verify via atomic force microscopy that dimensional structures have in fact been formed. Additionally the coverage ratio controlled by the concentration of the DNA monomer was analyzed to understand the lattice growth on the substrate. The DNA lattices were observed to start growing on the substrate at a concentration of around 1 nM (threshold) and to achieve full coverage at 10 nM (saturation concentration). Finally, the Raman spectra and the current–voltage characteristics of Zn2+-doped OLs were obtained in order to demonstrate the feasibility of using such methods to produce useful materials for nanodevices and biosensors. As [Zn2+] increases above the critical value of 0.5 mM, the Raman peaks gradually decrease. The resistance decreases up to the critical value of [Zn2+], and then decreases [Zn2+] continues to increase.

Assembly of a tile-based multilayered DNA nanostructure.

The Watson-Crick complementarity of DNA is exploited to construct periodically patterned nanostructures, and we herein demonstrate tile-based three dimensional (3D) multilayered DNA nanostructures that incorporate two design strategies: vertical growth and horizontal layer stacking with substrate-assisted growth. To this end, we have designed a periodically holed double-double crossover (DDX) template that can be used to examine the growth of the multilayer structures in both the vertical and horizontal directions. For vertical growth, the traditional 2D double crossover (DX) DNA lattice is seeded and grown vertically from periodic holes in the DDX template. For horizontal stacking, the DDX layers are stacked by binding the connector tiles between each layer. Although both types of multilayers exhibited successful formation, the observations with an atomic force microscope indicated that the DDX layer growth achieved with the horizontal stacking approach could be considered to be slightly better relative to the vertical growth of the DX layers in terms of uniformity, layer size, and discreteness. In particular, the newly designed DDX template layer provided a parallel arrangement between each domain with substrate-assisted growth. This kind of layer arrangement suggests a possibility of using our design scheme in the construction of other periodic structures.

Substrate-assisted 2D DNA lattices and algorithmic lattices from single-stranded tiles.

We present a simple route to circumvent kinetic traps which affect many types of DNA nanostructures in their self-assembly process. Using this method, a new 2D DNA lattice made up of short, single-stranded tile (SST) motifs was created. Previously, the growth of SST DNA assemblies was restricted to 1D (tubes and ribbons) or finite-sized 2D (molecular canvases). By utilizing the substrate-assisted growth method, sets of SSTs were designed as unit cells to self-assemble into periodic and aperiodic 2D lattices which continuously grow both along and orthogonal to the helical axis. Notably, large-scale (∼1 μm(2)) fully periodic 2D lattices were fabricated using a minimum of just 2 strand species. Furthermore, the ability to create 2D lattices from a few motifs enables certain rules to be encoded into these SSTs to carry out algorithmic self-assembly. A set of these motifs was designed to execute simple 1-input 1-output COPY and NOT algorithms, the space-time manifestations which were aperiodic 2D algorithmic SST lattices. The methodology presented here can be straightforwardly applied to other motifs which fall into this type of kinetic trap to create novel DNA crystals.

A methanol VOC sensor using divalent metal ion-modified 2D DNA lattices

Metal ion modified DNA synthesized by a substrate-assisted growth method were utilized for a VOC gas sensor. Co-DNA lattices with defined periodicity efficiently yield an enhancement in reflected intensities within TLV of methanol vapor selectively.

Energy band gap and optical transition of metal ion modified double crossover DNA lattices.

We report on the energy band gap and optical transition of a series of divalent metal ion (Cu(2+), Ni(2+), Zn(2+), and Co(2+)) modified DNA (M-DNA) double crossover (DX) lattices fabricated on fused silica by the substrate-assisted growth (SAG) method. We demonstrate how the degree of coverage of the DX lattices is influenced by the DX monomer concentration and also analyze the band gaps of the M-DNA lattices. The energy band gap of the M-DNA, between the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO), ranges from 4.67 to 4.98 eV as judged by optical transitions. Relative to the band gap of a pristine DNA molecule (4.69 eV), the band gap of the M-DNA lattices increases with metal ion doping up to a critical concentration and then decreases with further doping. Interestingly, except for the case of Ni(2+), the onset of the second absorption band shifts to a lower energy until a critical concentration and then shifts to a higher energy with further increasing the metal ion concentration, which is consistent with the evolution of electrical transport characteristics. Our results show that controllable metal ion doping is an effective method to tune the band gap energy of DNA-based nanostructures.

Quantitative analysis of molecular-level DNA crystal growth on a 2D surface

Crystallization is an essential process for understanding a molecule's aggregation behavior. It provides basic information on crystals, including their nucleation and growth processes. Deoxyribonucleic acid (DNA) has become an interesting building material because of its remarkable properties for constructing various shapes of submicron-scale DNA crystals by self-assembly. The recently developed substrate-assisted growth (SAG) method produces fully covered DNA crystals on various substrates using electrostatic interactions and provides an opportunity to observe the overall crystallization process. In this study, we investigated quantitative analysis of molecular-level DNA crystallization using the SAG method. Coverage and crystal size distribution were studied by controlling the external parameters such as monomer concentration, annealing temperature, and annealing time. Rearrangement during crystallization was also discussed. We expect that our study will provide overall picture of the fabrication process of DNA crystals on the charged substrate and promote practical applications of DNA crystals in science and technology.