Transmission Infrared Spectra of CH_3-, CD_3-, and C_(10)H_(21)-Ge(111) Surfaces

The surface chemistry of CH_3–, CD_3–, and C_(10)H_(21)–Ge(111) surfaces prepared through a bromination/alkylation method have been investigated by infrared spectroscopy. Well-ordered CH_3–Ge(111) surfaces could be prepared only if, prior to bromination, the surface was etched with 6.0 M HCl or with a two-step etch of H_2O_2 (1.5 M)/HF (5.1 M) followed by a short HF (6.0 M) etch. The etching method used to make the Ge precursor surface, and the formation of a bromine-terminated intermediate Ge surface, were of critical importance to obtain clear, unambiguous infrared absorption peaks on the methyl-terminated Ge surfaces. Polarization-dependent absorption peaks observed at 1232 cm^(–1) for CH_3–Ge(111) surfaces and at 951 cm^(–1) for CD_3–Ge(111) surfaces were assigned to the methyl “umbrella” vibrational mode. A polarization-dependent peak at 2121 cm^(–1) for CD_3–Ge(111) surfaces was assigned to the symmetric methyl stretching mode. Polarization-independent absorption peaks at 755 cm^(–1) for CH_3–Ge(111) and at 577 cm^(–1) for CD_3–Ge(111) were assigned to the methyl rocking mode. These findings provide spectroscopic evidence that the methyl monolayer structure on the alkylated Ge is well-ordered and similar to that on analogous Si(111) surfaces, despite differences in the composition of the precursor surfaces. The X-ray photoelectron spectra of CH_3–Ge(111) surfaces, however, were not highly dependent upon the etching method and showed a constant C 1s:Ge 3d ratio, independent of the etching method. The infrared spectra of C_(10)H_(21)–Ge(111) surfaces were also not sensitive to the initial etching method. Hence, while the final packing density of the alkyl groups on the surface was similar for all etch methods studied, not all methods yielded a well-ordered Ge(111)/overlayer interface

Chemical, Electronic, and Electrical Properties of Alkylated Ge(111) Surfaces

The use of Ge in semiconductor electronics has been constrained by the lack of a simple method of passivating the crystal surface. Toward that end, we have explored the utility of chemically bonded hydrocarbon monolayers. Alkylated Ge(111) surfaces have been prepared by addition of 1-alkenes to the H-terminated Ge(111) surface as well as by a two-step halogenation/alkylation procedure. The chemical compositions of the resulting methyl-, ethyl-, and decyl-terminated surfaces have been evaluated using X-ray photoelectron spectroscopy (XPS). Thermal addition of 1-decene produced hydrophobic surfaces with 0.3 ± 0.1 monolayer of Ge oxide detected by XPS, whereas no oxide was observed on the methyl-, ethyl-, or decyl-terminated surfaces that were prepared using the two-step halogenation/alkylation method. Methyl-terminated Ge(111) surfaces prepared by the two-step method displayed a well-resolved C 1s XPS peak at a binding energy of 284 eV, consistent with carbon bonded to a less electronegative element such as Ge. The electronic properties of all of the alkylated surfaces were characterized by measurements of the surface recombination velocity as a function of an externally applied gate voltage. Treatment of HF-etched Ge(111) surfaces with Br2 vapor, followed by reaction with alkylmagnesium or alkyllithium reagents, yielded air-stable surfaces that had surface recombination velocities of 100 cm s^(−1) or less under flat-band conditions. The field-dependent surface recombination velocity experiments indicated that, in contact with air, methyl-terminated n-type Ge(111) samples had a negative surface potential approaching 300 mV, in contrast to the oxidized Ge(111) surface, which exhibited a strongly positive surface potential under the same conditions. Mercury contacts to n-type methyl-, ethyl-, or decyl-terminated Ge(111) substrates that were alkylated using the two-step method formed rectifying junctions with barrier heights of 0.6 ± 0.1 eV, whereas no measurable rectification was observed for Hg contacts to p-type Ge(111) substrates that were alkylated by the two-step method, to n-type Ge(111) substrates that were alkylated through addition of 1-decene, or to oxidized n-type Ge(111) samples

Scanning tunneling microscopy studies of monolayer templates: alkylthioethers and alkylethers

Scanning tunneling microscopy has been used to determine the molecular ordering in stable, ordered monolayers formed from long-chain normal and substituted alkanes in solution on highly oriented pyrolytic graphite surfaces. Monolayers were initially formed using an overlying solution of either a symmetrical dialkylthioether or a symmetrical dialkylether. Initially pure thioether solutions were then changed to nearly pure solutions of the identical chain-length ether, and vice versa. The direct application of a pure solution of long-chain symmetrical ethers onto graphite produced a lamellate monolayer within which the individual molecular axes were oriented at an angle of ~65° to the lamellar axes. In contrast, a pure solution of long-chain symmetrical thioethers on graphite produced a monolayer within which the molecular axes were oriented perpendicular to the lamellar axes. When ethers were gradually added to solutions overlying pure thioether monolayers, the ethers substituted into the existing monolayer structure. Thus, the ether molecules could be forced to orient in the perpendicular thioether-like manner through the use of a thioether template monolayer. Continued addition of ethers to the solution ultimately produced a nearly pure ether monolayer that retained the orientation of the thioether monolayer template. However, a monolayer of thioether molecules formed by gradual substitution into an ether monolayer did not retain the 65° orientation typical of dialkylethers, but exhibited the 90° orientation typical of dialkylthioether monolayers. The thioethers and ethers were easily distinguished in images of mixed monolayers, allowing both an analysis of the distribution of the molecules within the mixed monolayers and a comparison of the monolayer compositions with those of the overlying solutions. Substitution of molecules into the template monolayer did not proceed randomly; instead, a molecule within a monolayer was more likely to be replaced by a molecule in the overlying solution if it was located next to a molecule that had already been replaced

Synthesis and Characterization of Mixed Methyl/Allyl Monolayers on Si(111)

The formation of mixed methyl/allyl monolayers has been accomplished through a two-step halogenation/alkylation reaction on Si(111) surfaces. The total coverage of alkylated Si, the surface recombination velocities, and the degree of surface oxidation as a function of time have been investigated using X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, and microwave conductivity measurements. The total coverage of alkyl groups, the rate of oxidation, and the surface recombination velocities of Si(111) terminated by mixed monolayers were found to be close to those observed for CH_3−Si(111) surfaces. Hence, the mixed-monolayer surfaces retained the beneficial properties of CH_3−Si(111) surfaces while allowing for convenient secondary surface functionalization

Two-Dimensional, Pyrazine-Based Nonlinear Optical Chromophores with Ruthenium(II) Ammine Electron Donors

Six new nonlinear optical (NLO) chromophores with pyrazinyl-pyridinium electron acceptors have been synthesized by complexing a known pro-ligand with electron donating {Ru^(II)(NH_3)_5}^(2+) or trans-{Ru^(II)(NH_3)_4(py)}^(2+) (py = pyridine) centers. These cationic complexes have been characterized as their PF_6^− salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. The visible d → π* metal-to-ligand charge-transfer (MLCT) absorptions gain intensity on increasing the number of Ru^(II) centers from one to two, but remain at constant energy. One or two Ru^(III/II) redox processes are observed which are reversible, quasi-reversible, or irreversible, while all of the ligand-based reductions are irreversible. Molecular first hyperpolarizabilities β have been determined by using hyper-Rayleigh scattering (HRS) at 1064 nm, and depolarization studies show that the NLO responses of the symmetric species are strongly two-dimensional (2D) in character, with dominant “off-diagonal” β_(zyy) components. Stark (electroabsorption) spectroscopic measurements on the MLCT bands also allow the indirect determination of estimated static first hyperpolarizabilities β_0. Both the HRS and the Stark-derived β_0 values increase on moving from mono- to bimetallic complexes, and substantial enhancements in NLO response are achieved when compared with one-dimensional (1D) and 2D monometallic Ru^(II) ammine complexes reported previously

Phosphine Functionalization of GaAs(111)A Surfaces

Phosphorus-functionalized GaAs surfaces have been prepared by exposure of Cl-terminated GaAs(111)A surfaces to triethylphosphine (PEt3) or trichlorophosphine (PCl3), or by the direct functionalization of the native-oxide terminated GaAs(111)A surface with PCl3. The presence of phosphorus on each functionalized surface was confirmed by X-ray photoelectron spectroscopy. High-resolution, soft X-ray photoelectron spectroscopy was used to evaluate the As and Ga 3d regions of such surfaces. On PEt3 treated surfaces, the Ga 3d spectra exhibited a bulk Ga peak as well as peaks that were shifted to 0.35, 0.92 and 1.86 eV higher binding energy. These peaks were assigned to residual Cl-terminated Ga surface sites, surficial Ga2O and surficial Ga2O3, respectively. For PCl3-treated surfaces, the Ga 3d spectra displayed peaks ascribable to bulk Ga(As), Ga2O, and Ga2O3, as well as a peak shifted 0.30 eV to higher binding energy relative to the bulk signal. A peak corresponding to Ga(OH)3, observed on the Cl-terminated surface, was absent from all of the phosphine-functionalized surfaces. After reaction of the Cl-terminated GaAs(111)A surface with PCl3 or PEt3, the As 3d spectral region was free of As oxides and As0. Although native oxide-terminated GaAs surfaces were free of As oxides after reaction with PCl3, such surfaces contained detectable amounts of As0. Photoluminescence measurements indicted that phosphine-functionalized surfaces prepared from Cl-terminated GaAs(111)A surfaces had better electrical properties than the native-oxide capped GaAs(111)A surface, while the native-oxide covered surface treated with PCl3 showed no enhancement in PL intensity

Crystalline nickel, cobalt, and manganese antimonates as electrocatalysts for the chlorine evolution reaction

The chlorine-evolution reaction (CER) is a common, commercially valuable electrochemical reaction, and is practiced at industrial scale globally. A precious metal solid solution of RuO_2 or IrO_2 with TiO_2 is the predominant electrocatalyst for the CER. Herein we report that materials comprised only of non-precious metal elements, specifically crystalline transition-metal antimonates (TMAs) such as NiSb_2O_x, CoSb_2O_x, and MnSb_2O_x, are moderately active, stable catalysts for the electrochemical oxidation of chloride to chlorine under conditions relevant to the commercial chlor-alkali process. Specifically, CoSb2Ox exhibited a galvanostatic potential of 1.804 V vs. NHE at 100 mA cm^(−2) of Cl_2(g) production from aqueous pH = 2.0, 4.0 M NaCl after 250 h of operation. Studies of the bulk and surface of the electrocatalyst and the composition of the electrolyte before and after electrolysis indicated minimal changes in the surface structure and intrinsic activity of CoSb_2O_x as a result of Cl2(g) evolution under these conditions

Response and Discrimination Performance of Arrays of Organothiol-Capped Au Nanoparticle Chemiresistive Vapor Sensors

The response and discrimination performance of an array that consisted of 20 different organothiol-capped Au nanoparticle chemiresistive vapor sensors was evaluated during exposure to 13 different organic vapors. The passivating organothiol ligand library consisted of collections of straight-chain alkanethiols, branched alkanethiols, and aromatic thiols. A fourth collection of sensors was formed from composites of 2-phenylethanethiol-capped Au nanoparticles and nonpolymeric aromatic materials that were coembedded in a sensor film. The organic vapors consisted of six hydrocarbons (n-hexane, n-heptane, n-octane, isooctane, cyclohexane, and toluene), three polar aprotic vapors (chloroform, tetrahydrofuran, and ethyl acetate), and four alcohols (methanol, ethanol, isopropanol, and 1-butanol). Trends in the resistance response of the sensors were consistent with expected trends in sorption due to the properties of the test vapor and the molecular structure of the passivating ligands in the sensor films. Classification algorithms including principal components analysis and Fisher’s linear discriminant were used to evaluate the discrimination performance of an array of such sensors. Each collection of sensors produced accurate classification of most vapors, with misclassification occurring primarily for vapors that had mutually similar polarity. The classification performance for an array that contained all of the sensor collections produced nearly perfect discrimination for all vapors studied. The dependence of the array size (i.e., the number of sensors) and the array chemical diversity on the discrimination performance indicated that, for an array of 20 sensors, an array size of 13 sensors or more produced the maximum discrimination performance