Photostimulated Pyrothermoelectric Coupling in Two-Dimensional Tin Monoselenide Enabling Zero-Biased Multimodal Transducers.

Despite the advancement of the Internet of Things (IoT) and portable devices, the development of zero-biased sensing systems for the dual detection of light and gases remains a challenge. As an emerging technology, direct energy conversion driven by intriguing physical properties of two-dimensional (2D) materials can be realized in nanodevices or a zero-biased integrated system. In this study, we unprecedentedly attempted to exploit the photostimulated pyrothermoelectric coupling of two-dimensional SnSe for use in zero-biased multimodal transducers for the dual detection of light and gases. We synthesized homogeneous, large-area 6 in SnSe multilayers via a rational synthetic route based on the thermal decomposition of a solution-processed single-source precursor. Zero-biased SnSe transducers for the dual monitoring of light and gases were realized by exploiting the synergistic coupling of the photostimulated pyroelectric and thermoelectric effects of SnSe. The extracted photoresponsivity at 532 nm and NO2 gas responsivity of the SnSe-based transducers corresponded to 1.07 × 10-6 A/W and 13263.6% at 0 V, respectively. To bring universal applicability of the zero-biased SnSe transducers, the wide operation bandwidth photoelectrical properties (visible to NIR) and dynamic current responses toward two NO2/NH3 gases were systematically evaluated.

Wafer-Scale Atomic Assembly for 2D Multinary Transition Metal Dichalcogenides for Visible and NIR Photodetection.

The tunable properties of 2D transition-metal dichalcogenide (TMDs) materials are extensively investigated for high-performance and wavelength-tunable optoelectronic applications. However, the precise modification of large-scale systems for practical optoelectronic applications remains a challenge. In this study, a wafer-scale atomic assembly process to produce 2D multinary (binary, ternary, and quaternary) TMDs for broadband photodetection is demonstrated. The large-area growth of homogeneous MoS2, Ni0.06Mo0.26S0.68, and Ni0.1Mo0.9S1.79Se0.21 is carried out using a succinct coating of the single-source precursor and subsequent thermal decomposition combined with thermal evaporation of the chalcogen powder. The optoelectrical properties of the multinary TMDs are dependent on the combination of heteroatoms. The maximum photoresponsivity of the MoS2-, Ni0.06Mo0.26S0.68-, and Ni0.1Mo0.9S1.79Se0.21-based photodetectors is 3.51 × 10-4, 1.48, and 0.9 A W-1 for 532 nm and 0.063, 0.42, and 1.4 A W-1 for 1064 nm, respectively. The devices exhibited excellent photoelectrical properties, which is highly beneficial for visible and near-infrared (NIR) photodetection.

Wafer-Scale Production of Two-Dimensional Tin Monoselenide: Expandable Synthetic Platform for van der Waals Semiconductor-Based Broadband Photodetectors.

A synthetic platform for industrially applicable two-dimensional (2D) semiconductors that addresses the paramount issues associated with large-scale production, wide-range photosensitive materials, and oxidative stability has not yet been developed. In this study, we attained the 6 in. scale production of 2D SnSe semiconductors with spatial homogeneity using a rational synthetic platform based on the thermal decomposition of solution-processed single-source precursors. The long-range structural and chemical homogeneities of the 2D SnSe layers are manifested using comprehensive spectroscopic analyses. Furthermore, the capability of the SnSe-based photodetectors for broadband photodetection is distinctly verified. The photoresponsivity and detectivity of the SnSe-based photodetectors are 5.89 A W-1 and 1.8 × 1011 Jones at 532 nm, 1.2 A W-1 and 3.7 × 1010 Jones at 1064 nm, and 0.14 A W-1 and 4.3 × 109 Jones at 1550 nm, respectively. The minimum rise times for the 532 and 1064 nm lasers are 62 and 374 µs, respectively. The photoelectrical analysis of the 5 × 5 SnSe-based photodetector array reveals 100% active devices with 95.06% photocurrent uniformity. We unequivocally validated that the air and thermal stabilities of the photocurrent yielded from the SnSe-based photodetector are determined to be >30 d in air and 160 °C, respectively, which are suitable for optoelectronic applications.

Highly Photosensitive Lead Sulfide Thin Films Grown by H2 S Free MOCVD Using a Single Source Metal-Organic Precursor.

High-quality lead sulfide (PbS) films are deposited on selected substrate chemistries by an H2 S-free metal-organic chemical vapor deposition (MOCVD) process using a single-source metal-organic complex (Pb(dmampS)2 ). The complex is synthesized via a salt metathesis reaction between PbCl2  and lithium 1-(dimethylamino)-2-methylpropane-2-thiolate (Li(dmampS)) in diethyl ether. Subsequent film deposition is conducted by a simple thermolysis process in the absence of H2 S, yet chemical and structural analysis confirm chemically stoichiometric and homogenous films. Mechanistic studies with electron impact mass spectroscopy (EIMS) and gas chromatography mass spectroscopy (GCMS) suggest the selective cleavage of C-S bonds in the complex as the reason for the facile PbS formation with negligible impurity incorporation. The high crystallinity, low hole concentrations, and charge transport properties comparable and in many cases superior to films produced by atomic layer deposition (ALD) testify to the quality of the films. Lastly, rigid and flexible photodetectors fabricated with the PbS films exhibit considerably high photocurrents, reliable switching characteristics, and high sensitivity over a broad spectral bandwidth, highlighting the potential for realizing practical broadband photodetectors.

Large Memory Window of van der Waals Heterostructure Devices Based on MOCVD-Grown 2D Layered Ge4 Se9.

Van der Waals (vdW) heterostructures have drawn much interest over the last decade owing to their absence of dangling bonds and their intriguing low-dimensional properties. The emergence of 2D materials has enabled the achievement of significant progress in both the discovery of physical phenomena and the realization of superior devices. In this work, the group IV metal chalcogenide 2D-layered Ge4 Se9 is introduced as a new selection of insulating vdW material. 2D-layered Ge4 Se9 is synthesized with a rectangular shape using the metalcorganic chemical vapor deposition system using a liquid germanium precursor at 240 °C. By stacking the Ge4 Se9 and MoS2 , vdW heterostructure devices are fabricated with a giant memory window of 129 V by sweeping back gate range of ±80 V. The gate-independent decay time reveals that the large hysteresis is induced by the interfacial charge transfer, which originates from the low band offset. Moreover, repeatable conductance changes are observed over the 2250 pulses with low non-linearity values of 0.26 and 0.95 for potentiation and depression curves, respectively. The energy consumption of the MoS2 /Ge4 Se9 device is about 15 fJ for operating energy and the learning accuracy of image classification reaches 88.3%, which further proves the great potential of artificial synapses.

Synthesis of 1T WSe2 on an Oxygen-Containing Substrate Using a Single Precursor.

The metallic property of metastable 1T' WSe2 and its promising catalytic performance have attracted considerable interest. A hot injection method has been used to synthesize 1T' WSe2 with a three-dimensional morphology; however, this method requires two or more precursors and long-chain ligands, which inhibit the catalytic performance. Here, we demonstrate the synthesis of 1T' WSe2 on a substrate by a simple heating-up method using a single precursor, tetraethylammonium tetraselenotungstate [(Et4N)2WSe4]. The triethylamine produced after the reaction is an electron donor that yields negatively charged WSe2, which is stabilized by triethylammonium cations as intercalants between layers and induces 1T' WSe2. The purity of 1T' WSe2 is higher on oxygen-containing crystalline substrates than amorphous substrates because the strong adhesion between WSe2 and the substrate can produce sufficient triethylammonium (TEA) intercalation. Among the oxygen-containing crystal substrates, the substrate with a lower lattice mismatch with 1T' WSe2 showed higher 1T' purity due to the uniform TEA intercalation. Furthermore, 1T' WSe2 on carbon cloth exhibited a more enhanced catalytic performance in the hydrogen evolution reaction (197 mV at 10 mA/cm2) than has been reported previously.

Novel Heteroleptic Tin(II) Complexes Capable of Forming SnO and SnO2 Thin Films Depending on Conditions Using Chemical Solution Deposition.

A new heteroleptic complex series of tin was synthesized by the salt metathesis reaction of SnX2 (X = Cl, Br, and I) with aminoalkoxide and various N-alkoxy-functionalized carboxamide ligands. The complexes, [ClSn(dmamp)]2 (1), [BrSn(dmamp)]2 (2), and [ISn(dmamp)]2 (3), were prepared from the salt metathesis reaction of SnX2 with one equivalent of dmamp; [Sn(dmamp)(empa)]2 (4), [Sn(dmamp)(mdpa)]2 (5), and [Sn(dmamp)(edpa)]2 (6) were prepared via the salt metathesis reaction using complex 2 with one equivalent of N-alkoxy-functionalized carboxamide ligand. Complexes 1-5 displayed dimeric molecular structures with tin metal centers interconnected by µ2-O bonding via the alkoxy oxygen atom. The molecular structures of complexes 1-5 showed distorted trigonal bipyramidal geometries with lone pair electrons in the equatorial position. Using complex 6 as a tin precursor, SnO x films were deposited by chemical solution deposition (CSD) and subsequent post-deposition annealing (PDA) at high temperatures. SnO and SnO2 films were selectively obtained under controlled PDA atmospheres of argon and oxygen, respectively. The SnO films featured a tetragonal romarchite structure with high crystallinity and a preferred growth orientation along the (101) plane. They also exhibited a lower transmittance of >52% at 400 nm due to an optical band gap of 2.9 eV. In contrast, the SnO2 films exhibited a tetragonal cassiterite crystal structure and an extremely high transmittance of >97% at 400 nm was observed with an optical band gap of 3.6 eV.

New Volatile Tantalum Imido Precursors with Carboxamide Ligands.

A series of Ta(V) t Bu-imido/N-alkoxy carboxamide complexes, TaCl2(N t Bu)(pyridine)(edpa) (1), TaCl(N t Bu)(edpa)2 (2), Ta(N t Bu)(edpa)3 (3), TaCl2(N t Bu)(pyridine)(mdpa) (4), and Ta(N t Bu)(mdpa)3 (5), were successfully synthesized by metathesis reactions between Ta(N t Bu)Cl3(py)2 and several equivalents of Na(edpa) (edpaH = N-ethoxy-2,2-dimethylpropanamide) and Na(mdpa) (mdpaH = N-methoxy-2,2-dimethylpropanamide). Furthermore, complexes 3 and 5 were simply transformed to new dimeric structures [Ta(µ2-O)(edpa)3]2 (6) and [Ta(µ2-O)(mdpa)3]2 (7) with the elimination of the N t Bu imido group by air exposure. Compounds 1-7 were characterized by 1H and 13C nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, elemental analysis, thermogravimetric analysis (TGA), and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis revealed that complexes 3 and 5 have a distorted pentagonal bipyramidal geometry around the central Ta atom, with three monoanionic bidentate N-alkoxy carboxamide ligands and one t Bu imido ligand saturating the coordination of tantalum ions. TGA revealed that complexes 3 and 5 had superior thermal characteristics and stability. These complexes could potentially be applied as precursors for tantalum oxide thin films.

Synthesis and Crystal Structures of New Strontium Complexes with Aminoalkoxy and ß-Diketonato Ligands.

New heteroleptic strontium complexes were synthesized using substitution reaction of bis(trimethylsilyl)amide of Sr(btsa)2·2DME with aminoalkoxide and ß-diketonate ligands. The complexes [Sr(bdmp)(btsa)]2·2THF (1), [Sr(bdeamp)(btsa)]2 (2), [Sr(dadamb)(btsa)]2 (3), [Sr(bdmp)(hfac)]3 (4), [Sr(bdeamp)(hfac)]3 (5), [Sr(dadamb)(hfac)]3 (6), and [Sr3(dadamb)4(tmhd)2] (7) were prepared and characterized by means of various analysis techniques such as Fourier transform infrared, NMR, thermogravimetric analysis, and elemental analysis. Complexes 1-3 were further structurally confirmed by single-crystal X-ray crystallography, and they displayed dimeric structures in which strontium atoms were connected by alkoxide oxygen atoms of the µ2 type. Compound 1 has a trigonal prismatic structure, whereas 2 and 3 have a distorted square pyramidal structure. In complexes 5-7, trimeric structures were obtained with strontium atoms connected by µ3-O bonds of alkoxide oxygen atoms and µ2-O bonds of alkoxide and ß-diketonate oxygen atoms. The crystal structures of 5, 6, and 7 showed distorted capped octahedral geometry, while 7 (middle Sr atom) displayed a distorted trigonal prism geometry. Complexes 5-7 displayed ∼70% mass loss in the temperature range from 25 to 315 °C.

Synthesis and characterization of novel zinc precursors for ZnO thin film deposition by atomic layer deposition.

A novel series of zinc complexes, [EtZn(dab)]2 (1), [EtZn(damb)]2 (2), [EtZn(damp)]2 (3), and [EtZn(dadb)]2 (4), were prepared via single-step substitution. Further, these were analyzed by nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR), elemental analysis, single crystal X-ray diffraction analysis, and thermogravimetric analysis (TGA). The X-ray crystallography analysis revealed that all complexes exist as dimeric structures with distorted tetrahedral geometry having zinc centers that are interconnected via µ2-O bonding of the aminoalkoxy oxygen atom. TGA and thermal analysis of the complexes showed high volatilities and stabilities at sublimation temperatures of 70, 95, 90, and 105 °C at 0.5 Torr for the respective compounds. Precursor 3 was successfully used for ZnO thin film deposition by ALD. A growth rate per cycle (GPC) of 0.125 nm per cycle was obtained at 200 °C and XPS analysis confirmed the growth of highly pure ZnO films without carbon and nitrogen impurities, while XRD analysis revealed the deposition of reasonably crystalline films. Additionally, the high transmittance and wide bandgap of the films are suitable for optoelectronic applications.

Tin(II) Aminothiolate and Tin(IV) Aminothiolate Selenide Compounds as Single-Source Precursors for Tin Chalcogenide Materials.

Tin aminothiolate compounds SnII(dmampS)2 (1) and SnIV(dmampS)2Se (2), where dmampS = 1-(dimethylamino)-2-methylpropane-2-thiolate, were synthesized. The molecular structures of 1 and 2 reveal a seesaw and distorted trigonal-bipyramidal geometry, respectively. The 1H NMR spectrum of 1 shows two types of resonances for the methyl groups of the α-carbon, methyl groups of the amino groups, and methylene groups at room temperature. On the other hand, the 1H NMR spectrum of 2 exhibits a single resonance for each of these groups. According to variable-temperature 1H NMR analysis, each of these two types of resonances occurring at relatively low temperatures (under 223 K for 1 and under 333 K for 2) are merged as a single resonance with increasing temperature. By using thermogravimetric and thermal decomposition analyses, the residual materials of compounds 1 and 2 are confirmed to be SnS and SnSSe, respectively. Compound 1 was subjected to a metal-organic chemical vapor deposition process, which allowed for the deposition of a dense and well-faceted orthorhombic phase SnS thin film on a SiO2/Si substrate with ∼200 nm thickness.

Heteroleptic manganese compounds as potential precursors for manganese based thin films and nanomaterials.

Heteroleptic manganese compounds, [Mn(tmhd)(TMEDA)Cl]2 (1), [Mn(tmhd)(dmamp)]2 (2), Mn2(tmhd)2(edpa)2(µ-THF) (3), [Mn(dmampea)(NEt2)]2 (4), and Mn(dmampea)(iPr-MeAMD) (5), were synthesized and characterized. Compound 5 was a volatile liquid. Structural analysis revealed that 1-4 were dimers. Compounds 1 and 3, 2, and 4 had distorted octahedral, distorted trigonal-bipyramidal, and distorted tetrahedral geometries around the Mn centers, respectively. Based on thermogravimetric analysis, the residues of 2 and 3 were expected to be MnO and Mn3O4, respectively. According to thermogravimetric analysis, 4 showed a higher residual value, whereas 5 exhibited a lower value than those expected for manganese nitrides.

A facile synthetic route to tungsten diselenide using a new precursor containing a long alkyl chain cation for multifunctional electronic and optoelectronic applications.

Single source precursors for coating and subsequent thermal decomposition processes enable a large-scale, low-cost synthesis of two-dimensional transition metal dichalcogenides (TMDs). However, practical applications based on two-dimensional TMDs have been limited by the lack of applicable single source precursors for the synthesis of p-type TMDs including layered tungsten diselenide (WSe2). We firstly demonstrate the simple and facile synthesis of WSe2 layers using a newly developed precursor that allows improved dispersibility and lower decomposition temperature. We study the thermal decomposition mechanism of three types of (Cat+)2[WSe4] precursors to assess the most suitable precursor for the synthesis of WSe2 layers. The resulting chemical and structural exploration of solution-processed WSe2 layers suggests that the (CTA)2[WSe4] may be a promising precursor because it resulted in the formation of high-crystalline WSe2. In addition, this study verifies the capability of WSe2 layers for multifunctional applications in optoelectronic and electronic devices. The photocurrent of WSe2-based photodetectors shows an abrupt switching behavior under periodic illumination of visible or IR light. The extracted photoresponsivity values for WSe2-based photodetectors recorded at 0.5 V correspond to 26.3 mA W-1 for visible light and 5.4 mA W-1 for IR light. The WSe2-based field effect transistors exhibit unipolar p-channel transistor behavior with a carrier mobility of 0.45 cm2 V-1 s-1 and an on-off ratio of ∼10.

Germanium Compounds Containing Ge═E Double Bonds (E = S, Se, Te) as Single-Source Precursors for Germanium Chalcogenide Materials.

New germanium chalcogenide precursors, S═Ge(dmamp)2 (3), S═Ge(dmampS)2 (4), Se═Ge(dmamp)2 (5), Se═Ge(dmampS)2 (6), Te═Ge(dmamp)2 (7), and Te═Ge(dmampS)2 (8), were synthesized from Ge(dmamp)2 (1) and Ge(dmampS)2 (2) using sulfur, selenium, and tellurium powders (dmamp = 1-dimethylamino-2-methyl-2-propanolate, dmampS = 1-dimethylamino-2-methylpropane-2-thiolate). Complexes 1 and 2 were synthesized from metathesis reactions of GeCl2·dioxane with 2 equiv of aminoalkoxide or aminothiolate ligands. Thermogravimetric analysis of complex 1 displayed good thermal stability and volatility. The molecular structures of complexes 2-8 from X-ray single crystallography showed distorted trigonal bipyramidal geometry at the germanium centers. Germanium chalcogenide materials (GeSe and GeTe) were obtained from the thermal decomposition of complexes 5, 6, and 8 in hexadecane. X-ray diffraction patterns exhibited that GeSe and GeTe had orthorhombic and rhombohedral phases, respectively. This study affords a facile method to easily prepare germanium chalcogenide materials using well-designed and stable complexes by thermal decomposition of single-source precursors in solution.

New Heteroleptic Cobalt Precursors for Deposition of Cobalt-Based Thin Films.

A new series of heteroleptic complexes of cobalt were synthesized using aminoalkoxide and ß-diketonate ligands. The complexes, [Co(dmamp)(acac)]2 (3), [Co(dmamp)(tfac)]2 (4), [Co(dmamp)(hfac)]2 (5), [Co(dmamp)(tmhd)]2 (6), and [Co(dmamb)(tmhd)]2 (7), were prepared by two-step substitution reactions and studied using Fourier transform infrared spectroscopy, mass spectrometry, elemental analysis, and thermogravimetric analysis (TGA). Complexes 3-7 displayed dimeric molecular structures for all of the complexes with cobalt metal centers interconnected by µ2-O bonding by the alkoxy oxygen atom. TGA and a thermal study of the complexes displayed high volatilities and stabilities for complexes 6 and 7, with sublimation temperatures of 120 °C/0.5 Torr and 130 °C/0.5 Torr, respectively.

Heteroleptic strontium complexes stabilized by donor-functionalized alkoxide and ß-diketonate ligands.

Heteroleptic complexes of strontium () were prepared by employing ß-diketonates and donor-functionalized alkoxides as coordinating ligands. The results illustrate the effect of alkoxide substituent groups on the overall structures of the complexes. The presence of a terminal methoxy group in the alkoxide ligands leads to the formation of trimeric complexes , whereas the substituents on the amine nitrogen prove to have less influence in determining the structure. The attempts to increase steric bulkiness of the aminoalkoxide ligands by introducing ethyl groups on the amine nitrogen and to the alkoxy carbon did not lead to a structural change from the dimeric form in but resulted in structurally interesting strontium complexes. In trimeric complexes , the three strontium atoms were held together by two µ3-O bonds using alkoxide oxygen atoms and two µ2-O bonds using a combination of alkoxide and ß-diketonate ligand oxygens. The strontium metal centers in these complexes exhibit seven-coordination states in and , whereas exhibits one six-coordinated and two seven-coordinated strontium metals in its structure. All of the complexes were characterized using FT-NMR, FT-IR, elemental analyses, and thermogravimetric (TG) analyses.

New heteroleptic magnesium complexes for MgO thin film application.

Novel heteroleptic magnesium complexes, [Mg(dmamp)(acac)]2 (), [Mg(dmamp)(tmhd)]2 (), [Mg(dmamp)(tfac)]2 (), and [Mg(dmamp)(hfac)]2 (), were successfully synthesized using dmamp and ß-diketonate as ligands. The thermogravimetric analyses and volatile studies of the complexes showed that the complexes and display high volatility and thermal stability. The single crystal X-ray study of the complexes reveals that both the complexes and were crystalized in the triclinic space group and as dimers, where magnesium atoms are in the pentacoordinate state with distorted trigonal bipyramidal geometry.

Synthesis of new heteroleptic strontium complexes.

A series of heteroleptic strontium complexes (1-9) using a combination of different aminoalkoxides and 2,2,6,6-tetramethyl-3,5-heptanedionate (tmhd) were prepared to examine the effect of the bulkiness and coordination ability of the aminoalkoxide ligand in these complexes as well as potential strontium precursors. All complexes were characterized by FT-IR, FT-NMR, elemental analyses, and thermo-gravimetric (TG) analyses. The crystal structure analyses of 1, 2, 4, and 5 demonstrate their stability in the dimer form and the unwillingness of the strontium atom to form more than six coordination bonds in these complexes. The complex 5 shows an unusual picture: the existence of one hexa-coordinated and one penta-coordinated strontium atom side by side in its dimer structure. The introduction of ether groups as coordination sites in complexes 6-9 led to a decrease in steric hindrance which resulted in the formation of the complex 7 as a tetramer. The complex 7 shows a unique Sr4O4 cubane core where oxygen atoms undergo µ3-bridging between strontium atoms. The TG analyses show that the complexes exhibit a step-wise decomposition character, with the major mass losses in the region 150-400 °C.

Application of soft lithography to metal-induced lateral crystallization of amorphous Si thin films involving self-assembly monolayers and atomic layer deposition.

Micro-contact printing of self-assembly monolayers (SAMs), i.e., octadecyl-trichlorosilane (OTS) was combined with self limiting atomic layer deposition in order to fabricate the selective deposition of nickel oxide on amorphous Si thin films. The localized nickel species facilitated metal-induced crystallization (MIC) and at later stages, metal-induced lateral crystallization (MILC) in amorphous Si thin films at the elevated temperatures ranging from 500 °C to 550 °C. The uniform coating of SAMs onto amorphous Si thin films was monitored using physical/chemical characterization, i.e., atomic force microscopy, electron microscopy, and Raman spectroscopy. The crystalline feature was found to be superior to the counterpart solid-phase crystallization. The effectiveness of SAMs appears to provide the microscale patterning in addition to the sophisticated control against nickel-species.

Metal-induced crystallization of amorphous Si thin films assisted by atomic layer deposition of nickel oxide layers.

Atomic layer deposition (ALD) of nickel oxide was applied to the nickel-induced crystallization of amorphous Si thin films. The nickel-induced crystallization was monitored as a function of annealing temperature and time using Raman spectroscopy. Since Raman spectroscopy allows for the numerical quantification of structural components, the incubation time and the crystallization rates were estimated as functions of the annealing temperature. The spatial locations of a nickel-based species, probably NiSi2, were investigated using X-ray photoelectron spectrometry. The formed NiSi2 seeds appeared to accelerate the crystallization kinetics in amorphous Si thin films deposited onto glass substrates. The ramifications of the atomic layer deposition are discussed with regard to large-panel displays, with special emphasis on the sophisticated control of the catalytic elements, especially nickel.