High-resolution inelastic neutron scattering and extensive first-principles calculations have been used to explore the low-temperature phase of the hybrid solar-cell material methylammonium lead iodide up to the well-known phase transition to the tetragonal phase at ca. 160 K. Contrary to original expectation, we find that the Pnma structure for this phase can only provide a qualitative description of the geometry and underlying motions of the organic cation. A substantial lowering of the local symmetry inside the perovskite cage leads to an improved atomistic model that can account for all available spectroscopic and thermodynamic data, both at low temperatures and in the vicinity of the aforementioned phase transition. Further and detailed analysis of the first-principles calculations reveals that large-amplitude distortions of the inorganic framework are driven by both zero-point-energy fluctuations and thermally activated cation motions. These effects are significant down to liquid-helium temperatures. For this important class of technological materials, this work brings to the fore the pressing need to bridge the gap between the long-range order seen by crystallographic methods and the local environment around the organic cation probed by neutron spectroscopy.
The distorted octahedral complexes [SnCl4{ n BuSe(CH2) n Se n Bu}] (n = 2 or 3), (1) and (2), obtained from reaction of SnCl4 with the neutral bidentate ligands and characterized by IR/Raman and multinuclear (1H, 77Se{1H} and 119Sn) NMR spectroscopy and X-ray crystallography, serve as very effective single source precursors for low pressure chemical vapor deposition (LPCVD) of microcrystalline, single phase tin diselenide films onto SiO2, Si and TiN substrates. Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM) imaging show hexagonal plate crystallites which grow perpendicular to the substrate surface in the thicker films, but align mostly parallel to the surface when the quantity of reagent is reduced to limit the film thickness. X-ray diffraction (XRD) and Raman spectroscopy on the deposited films are consistent with hexagonal SnSe2 (P3̅m1; a = b = 3.81 Å; c = 6.13 Å), with strong evidence for preferred orientation of the crystallites in thinner (0.5–2 μm) samples, consistent with crystal plate growth parallel to the substrate surface. Hall measurements show the deposited SnSe2 is a n-type semiconductor. The resistivity of the crystalline films is 210 (±10) mΩ cm and carrier density is 5.0 × 1018 cm–3. Very highly selective film growth from these reagents onto photolithographically patterned substrates is observed, with deposition strongly preferred onto the (conducting) TiN surfaces of SiO2/TiN patterned substrates, and onto the SiO2 surfaces of Si/SiO2 patterned substrates. A correlation between the high selectivity and high contact angle of a water droplet on the substrate surfaces is observed.
The indium(III) halo-bridged octahedral dimers [InX(2)(L-L)(mu-X)(2)InX(2)(L-L)] (X = Cl: L-L = MeS(CH(2))(2)SMe, MeSe(CH(2))(2)SeMe, (n)BuSe(CH(2))(2)Se(n)Bu), the ionic trans-[InX(2)(L-L)(2)][InX(4)] (X = Cl: L-L = (i)PrS(CH(2))(2)S(i)Pr; X = Br: L-L = MeS(CH(2))(2)SMe, (i)PrS(CH(2))(2)S(i)Pr, MeSe(CH(2))(2)SeMe), cis-[InCl(2)(thiamacrocycle)][InCl(4)] (thiamacrocycle = [12]aneS(4) or [14]aneS(4)) and the neutral, octahedral [InCl(3)([9]aneS(3))] and [InCl(3){MeC(CH(2)SMe)(3)}] were obtained in good yield by the reaction of 1:1 molar ratios of InX(3) with the ligand in anhydrous CH(2)Cl(2) solution. The distorted tetrahedral [InX(3)(Me(2)Se)] (X = Cl, Br or I) and [InX(3)(Me(2)Te)] (X = Br or I) were obtained from 1:3 and 1:2 molar ratios respectively of InX(3) and Me(2)E (E = Se or Te) also in CH(2)Cl(2). The ligand-bridged, distorted tetrahedral dimers [(InCl(3))(2){micro(2)-o-C(6)H(4)(CH(2)SMe)(2)}] and [(InCl(3))(2){micro(2)-MeTe(CH(2))(3)TeMe}] are formed even from a 1:1 In:ligand ratio. Key structure types were confirmed from crystal structures of [InCl(2){RSe(CH(2))(2)SeR}(micro-Cl)(2)InCl(2){RSe(CH(2))(2)SeR(2)}] (R = Me or (n)Bu), trans-[InX(2){(i)PrS(CH(2))(2)S(i)Pr}(2)][InX(4)] (X = Cl or Br), trans-[InBr(2){MeSe(CH(2))(2)SeMe}(2)][InBr(4)], cis-[InCl(2)([14]aneS(4))][InCl(4)] and [InBr(3)(Me(2)Se)]. The bulk complexes have been characterised by IR and Raman spectroscopy and microanalyses, while (1)H, (77)Se{(1)H} and (125)Te{(1)H} NMR spectroscopy show that the compounds are extremely labile in solution and undergo rapid dynamic exchange equilibria. Comparisons are drawn between these structurally rather diverse In(III) chalcogenoether complexes and the corresponding Ga(III) species (all of which are neutral and involve distorted tetrahedral coordination). The reaction of TlCl(3) with Me(2)E (E = Se or Te) shows that chlorination of Me(2)E rather than adduct formation occurs, while no reaction occurred between TlCl(3) and Me(2)S, consistent with Tl(III) being a very poor Lewis acid.
The reaction of RS(CH(2))(2)SR (R = Me, Et or (i)Pr) with NbF(5) produces [NbF(4){RS(CH(2))(2)SR}(2)][NbF(6)] which contain distorted eight-coordinate (dodecahedral) cations and octahedral anions, whereas RSe(CH(2))(2)SeR (R = Me or Bu(n)) form six-coordinate [(NbF(5))(2)(mu-RSe(CH(2))(2)SeR)]. Et(2)S and Me(2)Se (L) also form six-coordinate [NbF(5)(L)], but Me(2)S forms both [NbF(5)(Me(2)S)] and an eight-coordinate cation in [NbF(4)(Me(2)S)(4)][NbF(6)]. MeS(CH(2))(2)SMe forms eight-coordinate cations in [NbX(4){MeS(CH(2))(2)SMe}(2)][NbX(6)] (X = Cl or Br), but other complexes of the heavier halides including [NbX(5)(L)] and [(NbX(5))(2)(mu-L-L)] (L-L = RSe(CH(2))(2)SeR; o-C(6)H(4)(CH(2)SMe)(2) and o-C(6)H(4)(CH(2)SeMe)(2)) contain six-coordinate niobium. The very unstable [NbCl(5)(Me(2)Te)] was characterised spectroscopically, but all other attempts to form telluroether complexes resulted in decomposition, and NbI(5) was reduced even by thioethers. The complexes have been characterised by multinuclear NMR ((1)H, (19)F, (93)Nb, (77)Se or (125)Te), IR and UV/visible spectroscopy, and X-ray crystal structures are reported for [NbF(4){RS(CH(2))(2)SR}(2)][NbF(6)] (R = Me, (i)Pr), [NbF(4)(Me(2)S)(4)][NbF(6)], [NbCl(5)(Me(2)Se)], [NbBr(5)(Me(2)S)], [(NbCl(5))(2){o-C(6)H(4)(CH(2)SMe)(2)}] and [(NbCl(5))(2){MeSe(CH(2))(2)SeMe}]. All the complexes are very moisture sensitive and the fluoride complexes decompose slowly with fluorination of the neutral ligand.
Chemical strain effects arising from the large size mismatch between the two A-site cations results in a lowering of the symmetry from polar R3c to a polar Cc in Bi0.95Dy0.05FeO3.
The neutral complexes [GaCl 3 (E n Bu 2 )] (E = Se or Te), [(GaCl 3 ) 2 { n BuE(CH 2 ) n E n Bu}] (E = Se, n = 2; E = Te, n = 3), and [(GaCl 3 ) 2 { t BuTe(CH 2 ) 3 Te t Bu}] are conveniently prepared by reaction of GaCl 3 with the neutral E n Bu 2 in a 1:1 ratio or with n BuE(CH 2 ) n E n Bu or t BuTe(CH 2 ) 3 Te t Bu in a 2:1 ratio and characterized by IR/Raman and multinuclear ( 1 H, 71 Ga, 77 Se-{ 1 H}, and 125 Te{ 1 H}) NMR spectroscopy, respectively, all of which indicate distorted tetrahedral coordination at Ga. The tribromide analog, [GaBr 3 (Se n Bu 2 )], was prepared and characterized similarly. A crystal structure determination on [(GaCl 3 ) 2 { t BuTe(CH 2 ) 3 Te t Bu}] confirms this geometry with each pyramidal GaCl 3 fragment coordinated to one Te donor atom of the bridging ditelluroether, Ga−Te = 2.6356(13) and 2.6378(14) Å. The n Bu-substituted ligand complexes serve as convenient and very useful single source precursors for low pressure chemical vapor deposition (LPCVD) of single phase gallium telluride and gallium selenide, Ga 2 E 3 , films onto SiO 2 and TiN substrates. The composition and morphology were confirmed by SEM, EDX, and Raman spectroscopy, while XRD shows the films are crystalline, consistent with cubic Ga 2 Te 3 (F4̅ 3m) and monoclinic Ga 2 Se 3 (Cc), respectively. Hall measurements on films grown on SiO 2 show the Ga 2 Te 3 is a p-type semiconductor with a resistivity of 195 ± 10 Ω cm and a carrier density of 5 × 10 15 cm −3 , indicative of a close to stoichiometric compound. The Ga 2 Se 3 is also p-type with a resistivity of (9 ± 1) × 10 3 Ω cm, a carrier density of 2 × 10 13 cm −3 , and a mobility of 20−80 cm 2 / V·s. Competitive deposition of Ga 2 Te 3 onto a photolithographically patterned SiO 2 /TiN substrate indicates that film growth onto the conducting and more hydrophobic TiN is preferred.
The effects of surface oxidation on the capacitance of titanium nitride electrode surfaces are examined. Electrochemical oxidation was effective in increasing capacitance.
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