Nanocrystal Thin Films Research Articles

Control of electrical conductivity of highly stacked zinc oxide nanocrystals by ultraviolet treatment

Zinc oxide (ZnO) nanocrystals (NCs) were synthesized using a modified sol-gel method. Ultraviolet (UV) treatment was performed under various atmospheres on the highly stacked ZnO NCs. The prepared NCs were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, photoluminescence spectroscopy, and atomic force microscopy to investigate their structural, electrical, and electrochemical properties. Through these analyses, the effect of the UV treatment on the chemical and electrical characteristics of ZnO NCs was established. According to the analyses, the organic ligands in the NCs were decomposed, and the particles were densified. The mobility of UV-treated ZnO NCs thin films increased to 1.4 cm2/Vs, almost 2 orders higher than the UV untreated ZnO thin films. It was confirmed that the recombination from oxygen vacancies of ZnO could be controlled by UV irradiation. As decreased oxygen vacancies, the band gap of ZnO NCs was increased from 3.2 eV to 3.27 eV.

The Effects of ZnTe:Cu Back Contact on the Performance of CdTe Nanocrystal Solar Cells with Inverted Structure.

CdTe nanocrystal (NC) solar cells have received much attention in recent years due to their low cost and environmentally friendly fabrication process. Nowadays, the back contact is still the key issue for further improving device performance. It is well known that, in the case of CdTe thin-film solar cells prepared with the close-spaced sublimation (CSS) method, Cu-doped CdTe can drastically decrease the series resistance of CdTe solar cells and result in high device performance. However, there are still few reports on solution-processed CdTe NC solar cells with Cu-doped back contact. In this work, ZnTe:Cu or Cu:Au back contact layer (buffer layer) was deposited on the CdTe NC thin film by thermal evaporation and devices with inverted structure of ITO/ZnO/CdSe/CdTe/ZnTe:Cu (or Cu)/Au were fabricated and investigated. It was found that, comparing to an Au or Cu:Au device, the incorporation of ZnTe:Cu as a back contact layer can improve the open circuit voltage (Voc) and fill factor (FF) due to an optimized band alignment, which results in enhanced power conversion efficiency (PCE). By carefully optimizing the treatment of the ZnTe:Cu film (altering the film thickness and annealing temperature), an excellent PCE of 6.38% was obtained, which showed a 21.06% improvement compared with a device without ZnTe:Cu layer (with a device structure of ITO/ZnO/CdSe/CdTe/Au).

Investigation of the Chemical Effect of Solvent during Ligand Exchange on Nanocrystal Thin Films for Wearable Sensor Applications

Ligand exchange processes have been attracting tremendous interest and are necessary when fabricating nanocrystal (NC) thin films for various applications. As ligand exchange processes are based on...

Chemical transformation of solution-processed Ag nanocrystal thin films into electrically conductive and catalytically active Pt-based nanostructures

Efficient methods for the controlled syntheses of metal nanocrystals are important for emerging electronics and catalysis applications. In this report, we present a solution-based method for the fabrication of Pt-coated Ag nanocrystal (NC) thin films through the use of ligand-exchange and electroless deposition. We successfully prepared uniform or bumpy Ag@Pt core/shell structures, as well as Ag–Pt alloy structures, through control of the reducing agents. We first report the Ag–Pt alloy structures can be synthesized by low-temperature and solution-based process of post treatment that exhibited high catalytic activity toward the hydrogen evolution reaction.

Air-Stable CuInSe2 Nanocrystal Transistors and Circuits via Post-Deposition Cation Exchange.

Colloidal semiconductor nanocrystals (NCs) are a promising materials class for solution-processable, next-generation electronic devices. However, most high-performance devices and circuits have been achieved using NCs containing toxic elements, which may limit their further device development. We fabricate high mobility CuInSe2 NC field-effect transistors (FETs) using a solution-based, post-deposition, sequential cation exchange process that starts with electronically coupled, thiocyanate (SCN)-capped CdSe NC thin films. First Cu+ is substituted for Cd2+ transforming CdSe NCs to Cu-rich Cu2Se NC films. Next, Cu2Se NC films are dipped into a Na2Se solution to Se-enrich the NCs, thus compensating the Cu-rich surface, promoting fusion of the Cu2Se NCs, and providing sites for subsequent In-dopants. The liquid-coordination-complex trioctylphosphine-indium chloride (TOP-InCl3) is used as a source of In3+ to partially exchange and n-dope CuInSe2 NC films. We demonstrate Al2O3-encapsulated, air-stable CuInSe2 NC FETs with linear (saturation) electron mobilities of 8.2 ± 1.8 cm2/(V s) (10.5 ± 2.4 cm2/(V s)) and with current modulation of 105, comparable to that for high-performance Cd-, Pb-, and As-based NC FETs. The CuInSe2 NC FETs are used as building blocks of integrated inverters to demonstrate their promise for low-cost, low-toxicity NC circuits.

A PbSe nanocrystal vertical phototransistor with graphene electrode

Recently, low-voltage phototransistors have become promising candidates for optoelectronic applications. In this study, a general strategy for the fabrication of high-performance lead selenide (PbSe) nanocrystal (NCs)-based vertical phototransistor (VPT) using graphene as electrode was presented. Within the vertical geometry, channel length was determined by measuring the thickness of NCs thin film, thus enabling the device with ultrashort channel length (213 nm) without expensive lithography. Moreover, a high current density of 863 A cm−2 was obtained at low voltage. Utilizing the unique tunable Fermi energy (FE) of graphene, the vertical carrier transport could be effectively modulated by the Schottky barrier height between the graphene and PbSe NCs active material. As a result, the device exhibited excellent photoelectric characteristics, including a responsivity of 1.1 × 104 A W−1, an external quantum efficiency of 1.7 × 106%, a detectivity of 1.3 × 1010 Jones, and a temporal response of 7 ms at an illumination irradiance of 36 mW cm−2. Through analysis of energy levels, the carrier transport was modulated by the barrier height at the graphene-PbSe NCs interface, which is attributed to the tunable FE of graphene. Fabrication of VPT with high performance and low energy consumption represents a significant step forward for high-speed opticalswitch applications and future nanoscale complementary circuits.

Control of tunneling gap between nanocrystals by introduction of solution processed interfacial layers for wearable sensor applications

In this study, we introduce a strategy to introduce solution-processed interfacial layers in nanocrystal (NC) thin films to fabricate high-performance strain sensors. SiO2 interfacial layers are chemically introduced in ligand-exchanged Ag NC thin films to increase the tunneling gap or inter-particle distance between each Ag NC. In this way, the charge-transport mechanism is manipulated, leading to unique electromechanical properties with a high gauge factor. All solution-processed strain gauge sensors with high stability, durability, and sensitivity are fabricated. The sensor successfully measured delicate movements such as finger motions, demonstrating its possible application in electronic skin.

Depletion-Mediated Interfacial Assembly of Semiconductor Nanorods.

Electronic devices comprised of nanocrystal (NC) thin film are projected to demonstrate enhanced figure of merit if NC building blocks self-assemble into highly uniform, 2-dimensional (2-D) superstructures with long-range order. Despite intensive research efforts and remarkable progress, long-range assembly of colloidal anisotropic NCs into thin films with orientational and positional order has remained to be addressed. One of the most promising approaches is to dissolve excess free molecules into NC solution, which has enabled the formation of NC monolayers with exceptional quality at air/solution interface. Nevertheless, the assembly mechanism and the role of free molecules have not been comprehensively elucidated, restricting the use of the approach. Here, we find that the interfacial assembly of CdSe/CdS core/shell nanorods (NRs) results in various ordered structures in the presence of free oleic acid molecules. The structures include a bundle of standing NRs, a belt of multilayered lying NRs, and a monolayer smectic phase, obtained by simple change in density of surface ligands on the NRs. Experimental observation and theoretical calculation reveal that the assembly is initiated at the air/solution interface due to the preferential depletion attraction of NRs to the interface. However, subsequent growth is significantly altered depending on the ligand density that determines the relative magnitude of interface-NR depletion attraction to inter-NR attraction. Highly ordered structures of NRs, especially for the monolayer smectic phase, are promising as a polarized light-emitting layer for thin-film optical devices. In addition, our findings on the depletion-mediated NR assembly provide important and universal design criteria for 2-D structuring of NCs with diverse geometries and compositions.

Electrophoretically Deposited MoSe2/WSe2 Heterojunction from Ultrasonically Exfoliated Nanocrystals for Enhanced Electrochemical Photoresponse.

The solar response ability and low-cost fabrication of the photoanode are important factors for the effective output of the photoelectrochemical system. Modification of the photoanode by which its ability to absorb irradiation can be manipulated has gained tremendous attention. Here, we demonstrated the MoSe2, WSe2, and MoSe2/WSe2 nanocrystal thin films prepared by the liquid-phase exfoliated and electrophoresis methods. Atomic force microscopy and high-resolution transmission electron microscopy show that the liquid exfoliated nanocrystals have a few layered dimensions with good crystallinity. Scanning electron microscopy demonstrated uniform distribution and randomly oriented nanocrystals, having a homogeneous shape and size. X-ray diffraction, X-ray photoelectron spectroscopy, and Raman spectra confirm the equal contribution of MoSe2 and WSe2 nanocrystals in the formation of the MoSe2/WSe2 heterojunction. Because of superior absorption of MoSe2/WSe2 heterojunction in the visible region and type-II heterojunction band alignment, in situ measurement of heterojunction electrode shows almost 1.5 times incident photo-to-current conversion efficiency and photoresponsivity in comparison to individual material electrodes. Our result clearly indicates the influence of heterojunction formation between liquid exfoliated nanocrystals on effective separation of photogenerated exciton and enhances charge carrier transfer, which leads to the improvement in photoelectrochemical performance. Liquid exfoliated nanosheet-based heterojunction is attractive as efficient photoanodes for the photoelectrochemical systems.

Opportunities and challenges for electrochemistry in studying the electronic structure of nanocrystals.

We review the state-of-the-art of determining the electronic structure of nanocrystals in thin films by electrochemistry. Our core conclusion, the necessity of combining electrochemical with spectroscopic techniques, is illustrated with the holistic analysis of thin films of CdSe nanocrystals cross-linked with electroactive metal β-tetraaminophthalocyanines by differential pulse voltammetry, optical spectroscopy and potential modulated absorption spectroscopy. We show that the same nanocrystals cross-linked with phthalocyanines of different metal centers exhibit rather similar electrochemical signatures, but behave distinctly different in spectroelectrochemical investigations. We argue that in one case, namely CdSe nanocrystals cross-linked with Co β-tetraaminophthalocyanine, we find supporting evidence for the hybridization of energy levels at the organic/inorganic interface. This work suggests that spectroelectrochemistry is capable of revealing the electronic structure of complex nanomaterials, such as semiconductor nanocrystals functionalized with organic pi-systems.

In Situ Measurement and Control of the Fermi Level in Colloidal Nanocrystal Thin Films during Their Fabrication.

In engineering a high-performance semiconductor device, understanding of the Fermi level position is critical. Here, we demonstrate that open-circuit potential (OCP) measurements can be used to quantify the Fermi level in nanocrystal thin films in situ during their solution-based fabrication. We use this method to study the influence of (1) a metal contact and (2) nanocrystal surface termination on the Fermi level of the nanocrystal film, and find that oxidization or reduction of the nanocrystals as well as surface terminations with dipoles can be used to tune the Fermi level over large energy ranges. Finally, to emphasize the compatibility of the technique with device fabrication, we show that we can use blends of ligands to design the Fermi level landscape in a nanocrystal film. Our work highlights that OCP measurements can be used to gain insight into existing device operation and direct further optimization of optoelectronic devices.

Engineering the work function of solution-processed electrodes of silver nanocrystal thin film through surface chemistry modification

A solution-processable electrode is a key component in flexible electronics. Despite recent studies on silver nanocrystal (Ag NC)-based electrodes with high conductivity, the absence of a strategy to control the work function has limited the development of low-cost and high-performance electronic devices. In this report, we introduce a chemical route to manipulate the work function of solution-processed Ag NC-based electrodes. The structural, chemical, optical, and electronic properties, as well as the work functions, of the Ag NC thin films treated with three types of halide ligands (Cl−, Br−, and I−) were investigated. Ultraviolet photoelectron spectroscopy analysis shows that the work functions are shifted to 4.76, 4.43, and 4.04 eV when the ligands are changed to Cl−, Br−, and I−, respectively. The trend in the shift induced by the halide ligands matches the results of atomistic density functional theory calculations and scales with the strength of the dipoles formed by the electron transfer at the NC/ligand interfaces. To demonstrate the impact of our strategy in device applications, we fabricated all-NC-based thin-film transistors and complementary metal-oxide-semiconductor inverters. This study provides a fundamental understanding of the surface states of nanomaterials and also offers technological benefits for the construction of low-cost, high-performance electronic devices.

Structural and optical properties of metallic doped palladium sulfide thin films

The Addition of impurities and the nature of substrate are known to change the properties of any deposited thin films. In this work, the influence of doping on the structural and optical properties of PdS thin films grown by chemical bath method has been studied. Aluminum (Al) was used as the dopant for PdS thin films deposited at room temperature. Band gap energy (E g), and other optical parameters were determined from the optical transmission of the film. The estimated energy band gap for the films varied from 1.50 to 1.80 eV. Nanocrystal PdS thin films exhibited a tetragonal structure with average crystallite size of 60 nm. The results obtained prove that doping has profound and superficial effects on optical and structural properties of the deposited PdS thin films.

Microwave-Polyol Synthesis of Sub-10-nm PbS Nanocrystals for Metal Oxide/Nanocrystal Heterojunction Photodetectors

A rapid microwave-polyol technique is developed to grow bare-surface sub-10-nm lead sulfide (PbS) colloidal nanocrystals (NCs) of uniform size. Growth involves three distinct dynamical stages. PbS NCs homogeneously nucleate and undergo a fast growth process that spontaneously aggregates them into a continuous microstructure of PbS. Next, the interaction of low-power microwave irradiation with the NCs’ dipole moments along different crystallographic axes leads to the development of strain at the NCs’ grain boundaries, which ultimately causes dissociation of the aggregated microstructures into individual uniform-sized PbS NCs. The most distinctive feature of this growth technique is the bare nature and uniform size of the NCs produced. This gives the freedom to fabricate a highly packed NC thin film, which is essential for enhanced charge-transport properties. It simultaneously also precludes the need of undergoing a detrimental solid-state ligand-exchange process, which is indispensably required for casting thin films from conventional counterpart long-aliphatic-ligand-capped NCs. To realize the photosensitivity and charge-transport nature of these microwave-synthesized NCs, we fabricated a lateral heterojunction photoconductor and a phototransistor that work on the principal of electron transfer to the metal oxide layer. The photoconductor exhibits prominent multispectral photosensitivity in the visible region, demonstrating high external quantum efficiency and detectivity of 7.42 × 102% and 1.07 × 1011 jones, respectively. Further, it also shows superior photocurrent generation with respect to the conventional hot-injection-method-synthesized PbS NC-based photoconductor, indicating more efficient inter-NC charge transport in its NC thin film. The unencapsulated photoconductor exhibits a long air-storage lifetime, which reflects air stability of the device and PbS NCs. In addition to the photoconductor, the metal oxide/PbS heterojunction phototransistor also shows superior photosensitivity with a responsivity and a response time of 3 × 10–2A/W and 2.2 s, respectively.

Enhanced photodesorption from near- and mid-infrared plasmonic nanocrystal thin films

The authors show that the desorption rate of two model molecules, indole and benzoic acid, from thin films of indium tin oxide nanocrystals supporting near- and mid-infrared (0.33–0.48 eV) localized surface plasmon resonances (LSPRs) is enhanced by as much as 60% upon illumination with broadband infrared light. The desorption rate increases linearly with light intensity. No increase in the desorption rate is detected for undoped In2O3 nanocrystal thin films or when photons resonant with the LSPR are blocked. The authors study the desorption rate enhancement as a function of illumination intensity, LSPR energy, and isotopic substitution. Importantly, the authors demonstrate the accelerated desorption via in-coupling of light to LSPRs with energies well within the mid-infrared. Their work opens the door to using these low energy photons as choreographers of chemical processes and sets the stage for future mechanistic studies.

Efficient Blue and White Perovskite Light-Emitting Diodes via Manganese Doping

Summary Despite heavy research, blue perovskite nanocrystal LEDs have struggled to match the high efficiencies of their red and green cousins, particularly at wavelengths blue enough to meet the NTSC blue standard. One of the most critical problems is the low photoluminescence yield of the nanocrystals in thin films. Recently, manganese doping has been shown to increase the photoluminescence yield of the perovskite even as a decay pathway to a long-lived emissive state on the manganese ion is introduced. Here, we employ a two-step synthetic approach to carefully tune the manganese doping to increase the blue photoluminescence while preventing significant manganese emission, allowing for blue perovskite LEDs with quantum efficiencies over 2% that meet the NTSC standard. Manganese doping increases the photoluminescence yield and lifetime, reduces trap states, and makes the dots more monodisperse, reducing the emission bandwidth. Finally, we utilize perovskite nanocrystal downconverters to build an all-perovskite white LED.

Forming-free resistive switching in solution-processed silicon nanocrystal thin film

We report a forming-free resistive switching using a solution-processed silicon nanocrystal (Si NC) thin film. A Si NC thin film is formed on an ITO/glass substrate by spin-coating a colloidal Si NC solution in air. The Si NC thin film shows bipolar resistive switching without a forming process. Electrical characteristics at low temperatures and in various gas environments suggest that a non-stoichiometric SiOx shell on Si NCs contributes to the resistive switching. We propose that the origin of the resistive switching is a conductive filament of oxygen vacancies on the SiOx shell by an electric field.

Surface Engineering of Transparent Cellulose Nanocrystal Coatings for Biomedical Applications.

The concept of blood typing diagnostics using blood drops dried onto transparent cellulose nanocrystal thin film (∼35 nm) coatings has been demonstrated. The substrate onto which the blood drops are dried plays an important role in such tests, depending on surface composition, roughness, and wettability. The drying profile of three different fluid dispersions: model latex particles, reagent blood cells, and whole human blood was studied on a range of different surfaces, including cellulose nanocrystals (CNCs), regenerated cellulose, and several hydrophobic polymers, in order to understand the role of surface chemistry, roughness, and fluid dispersion properties. The morphology of these surfaces was investigated using atomic force microscopy, roughness was calculated, and wettability was explored via contact angle measurement. The morphology of dried drops of human blood on different cellulosic surfaces was compared in order to understand the importance of cellulose crystallinity. Well-defined dried blood drops were observed on random and aligned CNC surfaces, facilitating visualization of individual cells. A simple antibody-antigen test was used to demonstrate the effectiveness of the CNC substrate for blood testing, showing high and reproducible selectivity.

Variable range hopping conduction in ZnO nanocrystal thin films

Zinc oxide (ZnO) nanocrystal films are of interest for new applications in thin film transistors and as transparent conductive oxides. Previous work has concentrated on achieving highly conductive, metallic films. This work focusses on the less explored insulating to semi-insulating regime, which enables obtaining deeper insights into the roles of surface states and defect states trapped at the nanocrystal interfaces. We examine the effects of various post-deposition treatments including controlled dosing with ultraviolet light, filling the voids between nanocrystals with a matrix material deposited by atomic layer deposition, and thermal annealing of the nanocrystal films. Both Mott and Efros–Shklovskii variable range hopping are observed depending on the carrier concentration in the nanocrystals. Using the above post-treatments to transition the films between the two conduction mechanisms enables determining the Fermi level density of states and the electron localization length. To interpret our results, we propose a model based on the assumption of nanocrystals consisting of quasi-neutral cores surrounded by shells depleted by surface OH trap states. The model suggests that the primary source of the increased conductivity in ZnO nanocrystal films based on post-treatments is an increase in the ability to tunnel between nanocrystals due to a reduction of the distance between the quasi-neutral nanocrystal cores.

Efficient Light-Emitting Diodes Based on in Situ Fabricated FAPbBr3 Nanocrystals: The Enhancing Role of the Ligand-Assisted Reprecipitation Process.

In this paper, we reported the in situ fabrication of highly luminescent formamidinium lead bromide (FAPbBr3) nanocrystal thin films by dropping toluene as an anti-solvent during the spin-coating with a perovskite precursor solution using 3,3-diphenylpropylamine bromide (DPPA-Br) as a ligand. The resulting films are uniform and composed of 5-20 nm FAPbBr3 perovskite nanocrystals. By monitoring the solvent mixing of anti-solvent and precursor solution on the substrates, we illustrated the difference between the ligand-assisted reprecipitation (LARP) process and the nanocrystal-pinning (NCP) process. This understanding provides a guideline for film optimization, and the optimized films obtained through the in situ LARP process exhibit strong photoluminescence emission at 528 nm, with quantum yields up to 78% and an average photoluminescence lifetime of 12.7 ns. In addition, an exciton binding energy of 57.5 meV was derived from the temperature-dependent photoluminescence measurement. More importantly, we achieved highly efficient pure green perovskite based light-emitting diode (PeLEDs) devices with an average external quantum efficiency (EQE) of 7.3% (maximum EQE is 16.3%) and an average current efficiency (CE) of 29.5 cd A-1 (maximum CE is 66.3 cd A-1) by adapting a conventional device structure of ITO/PEDOT:PSS/TFB/perovskite film/TPBi/LiF/Al. It is expected that the in situ LARP process provides an effective methodology for the improvement of the performance of PeLEDs.