MANGANESE β-DIKETONATES
Manganese (II) bis(acetylacetonate) Mn(acac)2
M = 253.15, buff (dark. yel.) cryst., mp. 248-250°C
Mn(acac)2 for Mn nanoparticles by MOCVD
Manganese(II) acetylacetonate Mn(acac)2 (MnAA) was applied for
the preparation of Mn and MnOx nanoparticles by MOCVD. Growth experiments were performed both in inert atmosphere using N2 carrier gas (pyrolysis), as well as in oxidizing atmosphere at 2 and 10 vol. % of O2 in the reaction mixture (oxidation). Other growth
conditions were following: reactor temperature 500 – 1000 °C, oxygen concentration (cO2: 0, 2 to 10vol. %), reactor total flow rate (QR: 600 – 1000 cm3/min), precursor vapor pressure (P MnAA : 0.82
– 5.47 Pa). Mn(acac)2 precursor vapor pressure was controlled by the variation of the saturator temperature (TS) and it was calculated on the basis of experimental data of Gotze et al. (1970) from the equation: MnAA (Pa)
S133.322 ]10 [8.9661 - 4612.6 / T (K)].The particle production was monitored by scanning mobility particle sizer (SMPS, TSI model 3936), as well as by characterisation of particles deposited onto TEM grids using nanometer aerosol sampler (NAS)
and on Sterlitech Ag filters. Particle morphology was studied by HRTEM, crystallinity by selected area electron diffraction (SAED), XRD and by HRTEM; chemical composition by EDS connected to HRTEM and XPS. [[i]]
[i] Pavel MORAVEC, Jiří SMOLÍK, Snejana BAKARDJIEVA, Valeri V. LEVDANSKY, PROC. 13TH ANNUAL CONF. CZECH AEROSOL SOC., 25th–26th October 2012, Třeboň. , p.39-42, http://cas.icpf.cas.cz/download/Sbornik_VKCAS_2012.pdf#page=39
“NANOPARTICLE FORMATION BY THERMAL DECOMPOSITION AND
OXIDATION OF MANGANESE(II) ACETYLACETONATE”
Manganese bis(acetylacetonate) dihydrate Mn(acac)2(H2O)2
(a) Simultaneous TG/DTA of Mn(acac)2(H2O)2. (inset: molecular structure)
(b) electron impact mass spectrum of Mn(acac)2(H2O)2.
Manganese(II) acetylacetonate dihydrate or diaquobisacetylacetonatomanganese(II)] [Mn(acac)2(H2O)2 is a crystalline solid at room temperature, starting to sublime at ca 200°C, according to thermogravimetric analysis.
Mn(acac)2(H2O)2 was characterised by electron impact mass spectroscopy. According to the mass spectrum (figure 1(b)) Mn(acac)2(H2O)2 (m/z = 289), H2O is detached from the molecule producing Mn(acac)2 (m/z = 253), which reduces further to Mn(acac) (m/z = 154), and the ‘acac’ (m/z = 100) fragments. Fragments with higher molecular weights are expected to undergo further fragmentation to produce CHCO (m/z = 41), CH3CO (m/z =43), CO, the CH3-radical etc. The first two fragments are expected to decompose further to produce the CH3-group, CO, carbon and H2, or alternatively can form C2H2O (ketene), and CH3CHO (acetaldehyde).
The m/z value for CO (28) and the CH3-group (15) were too low to be detected, but several peaks such as those with m/z = 238, 139, and 85, which may be obtained when a CH3 group is detached from Mn(acac)2, Mn(acac)1, and the ‘acac’ fragment, respectively are observed clearly in the spectrum.
Thus, in the case of a MOCVD process conducted in the absence of a reactive gas (f.e. O2), only in inert atmosphere (Ar), the gaseous products are expected to be CO, H2, C2H6 (obtained from the unstable methyl radical), C2H2O (ketene), and CH3CHO (acetaldehyde).
Mn(acac)2(H2O) for Mn oxides by MOCVD
[Mn(acac)2(H2O)2 was investigated as precursor for MOCVD of manganese oxides.
Mn oxides-based layers were grown under Ar and O2 atmosphere at different substrate temperatures, reactor pressures, and O2 flow rates. The conditions used were : Deposition temperature 400–700◦C, process pressure 5 Torr, precursor vaporizer temperature 200◦C, carrier gas (Ar) flow 40 sccm, reactive gas (O2) flow: 1) no O2 flow, carrier gas only; 2) 1-5 sccm of O2, plus carrier gas); deposition time 10–90 min, substrates: Stainless steel (SS-316), ceramic alumina, Si(100), graphite.
The resulting films are characterized by Raman spectroscopy and XRD
for phase identification, XPS for quantitative compositional analysis, and SEM for morphological studies. Equilibrium thermodynamic analysis of the process was applied to correlate the composition of the films as function of CVD parameters, both in Ar and
O2 ambient. The nature of the C-rich composite manganese oxide coating obtained in the deliberate absence of O2, was examined. A phase stability diagram for the deposition in O2 atmosphere, predicting stability windows for the growth of different manganese
oxides for varying thermodynamic parameters, was prepared. [[i]]
[i]SUKANYA DHAR, A VARADE, S A SHIVASHANKAR , Bulletin of Materials Science, 2011, Vol 34, Iss.1, pp 11-18 Thermodynamic modeling to analyse composition of carbonaceous coatings of MnO and other oxides of manganese grown by MOCVD”
http://www.ias.ac.in/matersci/bmsfeb2011/11.pdf
Mn(acac)2(H2O) for Mn oxide/C composites by MOCVD
Manganese (II) bis(acetylacetonate) hydrate Mn(acac)2(H2O)2 was synthesized, characterized by elemental analysis (CHN), XRD, FTIR spectroscopy, mass spectroscopy, and thermal analysis. Mn(acac)2(H2O)2 was applied as a precursor for MOCVD of composite coatings of carbonaceous manganese MnOx (MnO, Mn2O3, Mn3O4 and MnO2), which are widely applied for electrochemical applications in dry cells, lithium-ion batteries and supercapacitors. Carbonaceous MnOx films were deposited by MOCVD on the SS-316, ceramic alumina and Si (111) substrates; the change of film properties by varying deposition parameters (substrate, reactor pressure, Ar carrier flow rate, deposition duration) was studied. Depositions were carried out either in Ar ambient (without any oxidant), or with O2 flow (using argon as carrier gas). MnOx films deposited in the absence of O2 were thick, black, and electrically conducting, indicating the presence of carbon. The growth rate followed a typical thermal pattern, with activation energy of ~ 1.7 eV. The deposited films were composed of MnO in a carbon-rich amorphous matrix, according to XRD, TEM/ED, Raman, FTIR and XPS. High-resolution SEM showed that films composed of very fine particles (4 – 10 nm), resulting in very large specific surface area of the film ((~2000 m2/g by volumetric BET measurement).
MnOx films deposited under oxygen flow were no longer black and were highly resistive, indicating the absence of C contamination in the film, as confirmed by Raman spectroscopy. Films obtained under oxygen flow were more crystalline and consisted of nanocrystalline composites of two manganese oxides (MnO and Mn3O4), according to XRD, FTIR and Raman spectroscopy. The grown MnO/C hydrated nanocomposite coatings grown on a conducting substrate such as SS-316 (current collector) were studied as electrodes for electrochemical capacitor applications. Electrochemical measurements were carried out for both the 3-electrode assembly (for basic aqueous electrolyte) and 2-electrode assembly (for gel polymer electrolyte) using cyclic voltammetry (CV), AC impedance and charge-discharge techniques. Maximum specific capacitance of 230 – 270 F/g at 1 mA/cm2 discharge current density were obtained for the MnO/C nanocomposite coating grown at 680oC. The Bode plot showed a maximum phase angle of around 74 – 82o, indicating capacitive behaviour. The MnO/C nanocomposite film showed a very small time constant (0.5 – 3 msec), which is good for high frequency applications. The pulse power figure of merit was ~650 – 2000 W/g. Capacitance determined for a large number of charge-discharge cycles (~20000), and at large current densities (50 mA/cm2) showed promising results. The energy density (5 - 32 Wh/kg) and power density (2 – 4 kW/kg) estimated from charge-discharge data at 1 mA/cm2 showed the potential of the nanocomposite MnO/C as electrode for superior capacitor devices.
Magnetoconductance in MnO/C Nanocomposite coatings deposited on Alumina was studied. Amorphous systems (like MnO/C composites wherein carbon is amorphous and MnO is nearly so) are highly symmetric condensed
phases, do not possessing long range translational or orientational order.; disorder in the system creates Anderson localized states just above the valence band, which lead to reduced electrical conductivity. Amorphous MnO/C systems showed either a small negative
magnetoresistance (~ 5%) or a small positive magnetoconductance (~ 7%) at very low temperatures (~ 10 K). According to transport and magnetotransport measurements on the MnO/C nanocomposite film grown on alumina, a giant negative MR (22.3%) at a temperature
as high as 100 K was found, which is unusual because pure MnO is anti-ferromagnetic and does not ordinarily show any magnetoresistance (MR). [[i]]
[i] Varade, Ashish, PhD Thesis, "MOCVD Of Carbonaceous MnO Coating : Electrochemical And Charge Transport Studies", etd AT Indian Institute of Science > Division of Chemical Sciences > Materials Research Centre (mrc) > http://hdl.handle.net/2005/999, http://etd.ncsi.iisc.ernet.in/handle/2005/999
Manganese (III) tris(acetylacetonate) Mn(acac)3
Manganese (III) tris(acetylacetonate) Mn(acac)3 (M = 352.17) is a black powder., mp. 159-161 °C (dec.) [[i], [ii]].
The dielectric properties of amorphous thin films of Mn(acac)3 deposited on Si(P) substrates by thermal
sublimation in vacuum were studied by X-ray fluorescence (using Al/Mn(acac)3/Si(P) metal–insulator–semiconductor devices). It was found that values of the relative permittivity of Mn(acac)3 films was ca. 30–40. The dc-electrical conduction in the complex film was studied at room temperature and in temperature range of (293–325 K).[[iii]]
[i] https://de.wikipedia.org/wiki/Mangan(III)-acetylacetonat
[ii] https://www.chemistry.wustl.edu/files/chemistry/imce/Mn-acetylacetonate-3.pdf
[iii] A.A. Dakhel, J. Non-Cryst. Solids, Vol.351, Iss.40–42, 2005, p.3204–3208
“ I–V Characteristics of tris(2,4-pentanedionato)manganese(III) thin films”
Mn(acac)3 for LaMnO3±δ by MOCVD
Manganese (III) tris(acetylacetonate) Mn(acac)3, in combination with La(tmhd)3, has been applied as precursors for the growth of LaMnO3±δ layers by low pressure
MOCVD. Mn(acac)3 was synthesized and analysed by thermogravimetric analysis. The sublimation activation energy of Mn(acac)3 (100.5 kJ mol−1) was pressure-independent (in the pressure range 0.06–3 kPa). (compare to 177 kJ mol−1
for La(thd)3). [[i]]
[i] G.L.Bertrand, G.Caboche, L-C.Dufour, Solid State Ionics, Vol.129, Iss.1–4, 2000, p.219, http://www.sciencedirect.com/science/article/pii/S0167273899003288
Manganese bis(hexafluoracetylacetonate) trihydrate Mn(hfac)2×3H2O
Trihydrate Mn(hfac)2×3H2O: M = 523.09, mp. 173°C (dec.)
Manganese bis(hexafluoracetylacetonate) TMEDA adduct Mn(hfac)2(TMEDA)
Manganese bis(hexafluoracetylacetonate) TMEDA adduct Mn(hfac)2•tmeda [(H-hfac = 1,1,1,5,5,5-hexafluoro-2,4-pentandione, tmeda = N,N,N′,N′-tetramethylethylendiamine)], was synthesized in a single-step reaction and characterized by elemental analysis, thermal analysis, and IR spectroscopy. The solid-state crystal structure of Mn(hfa)2•tmeda is mononuclear. The complex is thermally stable (according to the thermal analyses) and can be evaporated leaving <2% residue. The properties of Mn(hfac)2•tmeda were compared commercial Mn precursors, Mn(acac)2 and Mn(tmhd)3, respectively. Mn(hfa)2•tmeda is the first example of manganese(II) precursor that can be used in the liquid phase without decomposition, thus providing constant evaporation rates, even for long deposition times.
Mn(hfa)2•tmeda was successfully applied as precursor for the growth of Mn3O4 films by reduced-pressure MOCVD.[[i]]
[i] Zaira Lipani, Maria R. Catalano, P. Rossi, P. Paoli, G. Malandrino, Chem. Vapor Dep., 2013, Vol. 19, Iss. 1-3, p. 22–28, “ A Novel Manganese(II) MOCVD Precursor: Synthesis, Characterization, and Mass Transport Properties of Mn(hfa)2•tmeda”, http://onlinelibrary.wiley.com/doi/10.1002/cvde.201207017/abstract;jsessionid=B63704799B890DEB61CBE2C6952DE7A6.f02t03?deniedAccessCustomisedMessage=&userIsAuthenticated=false
Mn(hfac)2(TMEDA) for MnF2 and Mn3O4 by MOCVD
Applying Mn(hfac)2*tmeda as precursor for atmospheric pressure MOCVD, manganese difluoride (MnF2) nanorod assemblies were obtained (in contrast to hausmannite (Mn3O4) nanostructured films obtained under reduced pressure MOCVD), as determined by grazing incidence XRD and EDX. Both the MnF2 and Mn3O4 phases had nanostructure morphology, as determined by field-emission SEM.[[i]]
Mn(hfa)2·tmeda
was successfully applied for the preparation of “pompon-like” MnF2 nanorod assemblies by atmospheric pressure metalorganic chemical vapor deposition (AP-MOCVD) of MnF2 nanostructures. [[ii]]
[i]Maria R. Catalano, Graziella Malandrino, Physics Procedia, Vol. 46, 2013, p.118–126, EUROCVD 19 , “Multifunctional Manganese Single Source Precursor for the Selective Deposition of MnF2 or Mn3O4”, http://dx.doi.org/10.1016/j.phpro.2013.07.053
http://www.sciencedirect.com/science/article/pii/S1875389213005117
[ii] G. Malandrino, R.G. Toro, M. R. Catalano, M. E. Fragalà, P. Rossi, P. Paoli, European J. Inorg. Chem., 2012, Iss. 7, p.1021–1024, “Pompon-Like MnF2 Nanostructures from a Single-Source Precursor through Atmospheric Pressure Chemical Vapor Deposition”
Manganese tris(hexafluoracetylacetonate) Mn(hfac)3
Manganese tris(hexafluoracetylacetonate) Mn(hfac)3: M = ,
Manganese tris(hexafluoracetylacetonate) Mn(hfac)3 has been applied as oxidative agent for the synthesis of heterobimetallic β-diketonates InMn(hfac)3, CdMn2(hfac)6, and Hg2Mn2(hfac)6, prepared with quantitative yields by solid state redox reaction of Mn(hfac)3 with finely divided metallic In, Cd, or Hg. These molecules possess heterometallic structure representing Lewis acid–base interactions between diketonate oxygens of the [Mn(hfac)3]− groups and “naked” metal centers (In+, Cd2+, and Hg 2 2+ cations). and retain structure upon sublimation, as well as in solutions of non-coordinating solvents. Due to their volatitlity, they potentially can be used as precursors for the growth of corresponding mixed metal oxides by MOCVD.[[i]]
[i] H. Zhang, Bo Li, Evgeny V. Dikarev, J. Cluster Sci., 2008, Vol.19, Iss.1, p.311, “Mn(III) Hexafluoroacetylacetonate as an Oxidative Agent in the Synthesis of Heterobimetallic β-Diketonates”, http://link.springer.com/article/10.1007/s10876-007-0174-1
Mn(thd)2 for Mn-doped ZnO by MOCVD
Manganese bis(2,2,6,6-tetramethyl-3,5-heptanedionate) Mn(thd)2, added to the THF solution of Zn(tmhd)2 (total concentration 0.025M), was applied as precursor for the growth
of Mn-doped ZnO thin films by MOCVD on c-plane sapphire and Si(100) substrates. The Mn concentration in the films varied by adjusting the Zn and Mn precursor flow rates during the deposition; films with higher Mn content appered more yellowish. Nitrogen was
used as a carrier gas, and oxygen was added for better oxidation. The thickness of ZnO films had a linear relationship with partial deposition pressure in the range of 5–60 Torr, what usually indicates a feed rate limited condition during the deposition.
However, changing the precursor flow rate at 50–100 g/h did not significantly alter the film thickness at a constant pressure. Deposition at a reactor pressure of 60 Torr resulted in a 1 Å/ s growth rate. The optimal growth conditions were: substrate
temperature 450°C, Mn(thd)2 and Zn(thd)2 vaporization temperature 245°C, reactor pressure 60 Torr, O2 flow 400 sccm, Ar flow 2000 sccm, N2 flow 100 sccm, Mn(thd)2 flow rate 5–20g/min, Zn(thd)2 flow rate 50g/min, growth rate 1Å/s, substrate
rotation 300 rpm, deposition time 20min. The ion beam, surface, and microstructural properties of undoped ZnOfilms vs. Mn-doped ZnO films were compared. For Mn doping up to ∼4.5 at. %
suppression of ZnO conductivity was observed. The presence of Mn2+, as determined by XPS, correlated with the reduction in conductivity. Variable-temperature Hall effect measurements yielded activation energy of 170 meV, consistent with deep donors in the
bulk or at the interface, suggesting that the incorporation of substitutional Mn suppresses the formation of native defects such as oxygen vacancies. [[i],[ii]]
[i] W. M. Hlaing Oo, L.V. Saraf, M.H. Engelhard, V. Shutthanandan, L. Bergman, J. Huso, M.D. McCluskey, J.Appl. Phys. 105, 013715 (2009); http://dx.doi.org/10.1063/1.3063730
http://scitation.aip.org/content/aip/journal/jap/105/1/10.1063/1.3063730
“Suppression of conductivity in Mn-doped ZnO thin films”
[ii] WMH Oo, LV Saraf, MH Engelhard, 2007 Annual Report , “Ion Beam and Surface Analysis of Conductivity Suppressed Mn Doped ZnO Thin Films Grown by MOCVD”, http://www.osti.gov/scitech/biblio/934410#page=134
Manganese tris(2,2,6,6-tetramethylheptane-3,5-dionate) Mn(thd)3
Manganese tris(2,2,6,6-tetramethyl-3,5-heptanedionate) Mn(thd)3 (or Mn(DPM)3 ) as a usual precursor for MOCVD of Mn-contaning layers.
Highly pure Mn(thd)3 was synthesized (by reaction of Mn(NO3)3 and ethanolic solution of in situ prepared Na(thd)), and characterized by elemental analysis, 1H-NMR, mass spectroscopy, and TGA/DSC. The thermal decomposition behavior of Mn(thd)3
was found to be sensitive to the ambient gases, (f.e. oxygen atmosphere is accelerate the decomposition and oxidation of the complex. According to mass spectroscopic analysis at elevated temperature, one of the three DPM groups in Mn(DPM)3 is dissociating
primarily, following with dissociation of +tBu and +OCCH2COtBu groups in sequence. It can be interpreted by the difference of metal ion radius. The kinetic parameters of activation energy and frequency factor were determined by calculations based on experimental
isothermal thermogravimetric data.[[i]]
[i]R.Yan, W. Huang, Q.Wang, Y. Jiang, Ionics, 2009, Vol.15, Iss.5, pp 627-633, Synthesis, characterization, and kinetic study of Mn(DPM)3 used as precursor for MOCVD,http://link.springer.com/article/10.1007/s11581-009-0316-6, http://link.springer.com/article/10.1007/s11581-009-0316-6#page-2
The decomposition behavior of several M(DPM)n complexes, including Mn(thd)3, was studied in detail with infrared spectroscopy and mass spectrometry. The results showed that the chemical bonds in these
compounds dissociated generally following the sequence of C−O > M−O > C−C(CH3)3 > C−C and C−H at elevated temperatures. The decomposition processes of M(DPM)n were strongly influenced by the coordination number and central
metal ion radius; the products of decomposition in air atmosphere varied from metal oxides to metal carbonates associated for different M(DPM)n.[[i]]
[i] Yinzhu Jiang, Mingfei Liu, Yanyan Wang, Haizheng Song, Jianfeng Gao, G. Meng, J. Phys. Chem. A, 2006, 110 (50), pp 13479–13486, DOI: 10.1021/jp064010j, “Decomposition Behavior of M(DPM)n (DPM = 2,2,6,6-Tetramethyl-3,5-heptanedionato; n = 2, 3, 4)” http://pubs.acs.org/doi/abs/10.1021/jp064010j
Mn(thd)3 for MnOx films growth by MOCVD
Tris(dipivaloylmethanato)manganese [Mn(DPM)3] (Mn(thd)3) was applied for the growth of manganese oxide films by liquid delivery MOCVD. The behavior of Mn(DPM)3 in the gas phase under actual
CVD conditions was analyzed by in situ IR absorption spectroscopy; the temperature dependence of the IR absorption indicated that Mn(DPM)3 was decomposed in the gas phase under the actual deposition conditions; the correlation between the thermal gas phase
decomposition of Mn(DPM)3 and MnOx film deposition was discussed. When the substrate temperature was raised >360°C, the growth rate decreased, synchronized with the decrease of the IR absorption by Mn(DPM)3 in the gas phase. The oxidation state of Mn
in the deposited films was studied by high-resolution XRF spectroscopy, no significant difference in the Mn oxidation state in the deposited films and Mn(DPM)3 was found.[[i]]
[i] Toshihiro Nakamura, Ryusuke Tai, Takuro Nishimura, K. Tachibana
J. Electrochem. Soc. 2005, vol. 152, iss.9, C584-C587, doi: 10.1149/1.1972181
http://jes.ecsdl.org/content/152/9/C584.short
Spectroscopic Study on Metallorganic Chemical Vapor Deposition of Manganese Oxide Films
Mn(thd)3 for YMnO3 on Si/SiO2 by flash evaporation MOCVD
Manganese tris(2,2,6,6-tetramethyl-3,5-heptanedionate) Mn(thd)3 (in combination with electronic grade Y(thd)3, both dissolved in a 1 : 1 ratio in tetraglyme solvent) was applied as precursor for the growth of YMnO3 (YMO) thin films on thermally oxidized p-type Si(100) substrates by flash evaporation MOCVD (using precursor solutions dissolved on
organic solvent). Yttrium manganate (YMO) thin films were prepared on SiO2 buffered silicon as a candidate for ferroelectric transistor random access memory (FeTRAM). The films were deposited at low temperature and post annealed to crystallize the c-axis oriented
hexagonal YMO phase; oxygen content and substrate temperature were the major parameters determining c-axis orientation. The electrical characteristics of the obtained Pt/YMO/Pt structures were: Pr (remnant polarization) 2 μ C/cm2. ϵ (dielectric constant) 20, a coercive field of approximately10 kV/cm. Fatigue stress cycling showed no degradation of films up to 1011 cycles. It was found that a top buffer layer of 30 nm ZrO2 helped to reduce the leakage current of Pt/top buffer/YMO/SiO2/Si
stack to 10− 7 A/cm2 and improved the C-V memory window from 0.2 V to 2 V.[[i], [ii] ]
[i]D. KIM, D. KLINGENSMITH, D. DALTON, V. OLARIU, F. GNADINGER, M. RAHMAN, A. MAHMUD, T. S. KALKUR, Integrated Ferroelectrics: An International Journal, Vol. 68, Issue 1, 2004, p. 75-84 , DOI: 10.1080/10584580490895671, C -Axis Oriented MOCVD YMnO3 Thin Film and Its Electrical Characteristics in MFIS FeTRAM
[ii]D. Kim, D. Killingensmith, D. Dalton, V. Olariu, F. Gnadinger, M. Rahman, A. Mahmud, T.S. Kalkur, Mater. Lett., 2006, Vol. 60, Iss.3, p.295–297
http://www.sciencedirect.com/science/article/pii/S0167577X0500830X
Ferroelectric properties of YMnO3 films deposited by metalorganic chemical vapor deposition on Pt/Ti/SiO2/Si substrates
Mn(thd)3 for YMnO3 on Si and SrTiO3 by pulsed liquid injection MOCVD
Tris(2,2,6,6-tetramethyl-3,5-heptanedionato)manganese Mn(thd)3, combined with Y(thd)3, was applied for the growth of YMnO3 films on Si substrates by pulsed liquid injection MOCVD process (with injector opening time, frequency of injection, and the moving belt speed being the parameters for process optimisation). Polycrystalline single phase YMnO3 films were obtained for an optimal Mn/Y ratio in the injected solution: either amorphous, metastable orthorhombic, and/or hexagonal YMnO3 phases were obtained depending on the growth temperature and precursors ratio, as determined by XRD and TEM.
For the YMnO3 films grown on single crystal SrTiO3
substrates, pure epitaxial orthorhombic YMnO3 phase was obtained according to XRD; columnar growth films microstructure was found by SEM and TEM, with each columnar grain growing epitaxially with three possible orientations.[[i]]
[i] I. Iliescu, M. Boudard, S. Pignard, L. Rapenne, P. Chaudouët & H. Roussel,
Phase Transitions: A Multinational Journal, Vol. 86, Issue 11, 2013, p. 1094-1103, “Growth and structural characterization of YMnO3 thin films grown by pulsed liquid injection MOCVD on Si and SrTiO3 substrates”, DOI: 10.1080/01411594.2012.754443
http://www.tandfonline.com/doi/abs/10.1080/01411594.2012.754443#.U07vqKKnTZw
Mn(thd)3 for CeMnO3 by MOCVD
Manganese (III) tris-tetramethylheptanedionate Mn(thd)3, combined with Ce(thd)4,both dissolved in tetrahydrofuran (THF) solvent, was applied for the growth of CeMnO3 thin films by MOCVD. The preferred deposition conditions for depositing CeMnO3 were: deposition temperature 650° C, chamber pressure 20 Torr, rotational speed 900 rpm, gas flow rates Ar: 1,000 sccm, O2: 3,750 sccm , evaporator dome and shell temperature 333° C, line temperatures 345° C, evaporator carrier gas flow rate Ar: 150 sccm; typical deposition time for 250 nm thick film: 27 min.
After deposition, the CeMnO3 ferroelectric films were annealed in O2 at temperatures around
800 to 950° C, in order to form the proper ferroelectric phase. The thickness of the interfacial layer slightly increased upon anneal, which was advantageous, because it improves the quality and reliability of this important oxide layer. The relatively
high anneal temperature, usually detrimental in usual ferroelectric memory devices, is not a problem since the ferroelectric CeMnO3 films are inserted into the process flow early, prior to source and drain formation. [[i]]
[i] Fred P. Gnadinger, US 7030435 B2, 2006; http://www.google.com/patents/US7030435
“Single transistor rare earth manganite ferroelectric nonvolatile memory cell”
Mn(thd)3 for NdMnO3 by MOCVD
Mn(tmhd)3 (combined with Nd(tmhd)3), both dissolved in 1,2 dimethoxyethane solvent (total concentration 0.02 mol/l), was applied for the deposition of lacunar Nd1-xMnO3-δ thin films
by liquid source MOCVD on (001) SrTiO3, LaAlO3 and Si substrates. Optimal growth conditions were determined. Thin films grown on STO and LAO substrates were single crystalline epitaxial, according to TEM and XRD. Magnetic transition temperatures (Tc) of the
as-grown STO films were determined by squid magnetometer measurements and compared to the bulk values (typically 100K). A complicated magnetic behavior close to the one observed in bulk samples was found: magnetization curves obtained under different applied
magnetic fields indicated a possible reverse of the magnetization sign at low temperatures.[[i]]
[i] N. Ihzaz, M. Boudard, L. Rapenne, H. Roussel, S. Pignard and M. Oumezzine, EPJ Web of Conferences 29, 00024 (2012),http://dx.doi.org/10.1051/epjconf/20122900024, “Physical and structural studies of chemical Vapor deposited lacunar neodymium manganite thin films”, http://epjwoc.epj.org/articles/epjconf/pdf/2012/11/epjconf_emm2012_00024.pdf
Mn(thd)3 for LaMnO3 by MOCVD
Mn(thd)3, in combination with La(thd)3, was successfully applied for the growth of lacunar La1-xMnO3-δ films by liquid-injection MOCVD. The influence of varying (P[O2]–T) conditions
on the films structure was studied by means of XRD and TEM; the phase relations of lanthanum manganite with manganese oxide phases (MnO, Mn3O4) were discussed. Tuning of TC via the concentration of La vacancies allowed to abtain significant magnetoresistance
at RT (~10% in a 1 T field).[[i,ii]]
[i]A. Bosak, C. Dubourdieu, M. Audier, J.P. Sénateur, J. Pierre, Appl. Phys. A, 2004, Vol.79, Iss.8,p.1979-1984, ”Compositional effects on the structure and magnetotransport properties of lacunar La1-xMnO3-δ films (x>0) grown by MOCVD”,http://link.springer.com/article/10.1007/s00339-003-2179-4
http://link.springer.com/article/10.1007/s00339-003-2179-4#page-2
[ii] S.Pignard,H.Vincent,M.Audier,J.Kreisel,G.Metellus, J.P.Senateur, J.Pierre, J.L.Hazemann, Nano-Crystalline and Thin Film Magnetic Oxides, NATO Sci. Series Vol72, 1999, p.59, Hexaferrite and Manganite Films Obtained by Injection - MOCVD Process http://link.springer.com/chapter/10.1007/978-94-011-4493-3_4, http://link.springer.com/chapter/10.1007/978-94-011-4493-3_4#page-1
Polycrystalline self-doped La1−xMnO3 films were prepared by liquid injection MOCVD, and evaluated for the fabrication of single-segment magnetoresistive magnetic field sensors based on a giant magnetoresistance (GMR) effect. The low field GMR sensitivity La1−xMnO3 films at liquid N2 temperature ranged from 0.4 to 0.7%/mT, depending on the deposition temperature. A method, based on the measurement of persistent low magnetic field near the surface of high-Tc superconducting tape was proposed, potentially useful for monitoring the BSCCO/Ag superconducting tapes quality with a tiny filament structure.[[i]]
[i] J Bydžovský, I Vávra, K Fröhlich, M Polák,V Šmatko, E Kovácová, P Paškevic, Sensors and Actuators A: Physical, 2001, Vol.91, Iss.1–2, p.21-25, Application of La1−xMnO3 giant magnetoresistance sensors for testing of high-TC superconducting tapes, http://www.sciencedirect.com/science/article/pii/S092442470100499X
Mn(thd)3 for (La,Ca)MnO3 by liquid delivery MOCVD
Mn(thd)3 , dissolved together with La(thd)3 and Ca(thd)2 in an organic solvent, was applied as precursor for the deposition of (La0.8Ca0.2)MnO3 thin films on LaAlO3 substrates by single-liquid-source
MOCVD. Depositions were performed at substrate temperatures 600-700°C and an O2 partial pressure 1.2 Torr. A large magnetoresistance change (ΔR/RH) of −550% was observed at 270 K in (La0.8Ca0.2)MnO3 thin films. The mechanism for the large magnetoresistance
change was discussed.[[i]]
[i] Y.Q. Li, J. Zhang, S. Pombrik, S. DiMascio, W. Stevens, Y.F. Yan, N.P. Ong, J. Mater. Research, 1995, vol. 10, iss.09, pp 2166-2169; “In situ single-liquid-source metal-organic chemical vapor deposition of (La0.8Ca0.2)MnO3 giant magnetoresistive films”, DOI: http://dx.doi.org/10.1557/JMR.1995.2166
http://journals.cambridge.org/action/displayAbstract?fromPage=online&aid=8160339
Mn(thd)3 for (Pr,Ca)MnO3, (La,Ca)MnO3 by MOCVD
The solution of solid precursor Mn(tmhd)3 (combined with Ca(tmhd)2 and Pr(tmhd)3 (or Pr(OiPr)3/or La(tmhd)3)) in a mixed solvent
of butyl ether and tetraglyme was applied as liquid precursor for the growth of (Pr,Ca)MnO3 (or (La,Ca)MnO3) thin films by MOCVD. This liquid precursor was injected into a vaporizer and the resulting vapor introduced into the MOCVD chamber, where O2 was also
introduced which reacted forming a PCMO film on the surface of the substrate.[[i]]
[i] WW Zhuang, ST Hsu, W Pan , US Patent 6,887,523, 2005
http://www.google.com/patents/US6887523, “ Method for metal oxide thin film deposition via MOCVD”
Mn(thd)3 for (Pr,Ca)MnO3 by liquid delivery MOCVD
Tris(dipivaloylmethanato)manganese [Mn(DPM)3] (or Mn(thd)3), combined with [Pr(DPM)3] and [Ca(DPM)2] was dissolved in tetrahydrofuran (at a concentration of 0.1 mol/l) and the solution vaporized in a vaporizer, then carried the vaporized source was transported by 200 sccm N 2 carrier gas into the MOCVD reactor, where Pr1−xCaxMnO3 (PCMO) films were deposited on Pt/SiO2/Si substrates by MOCVD using in situ IR spectroscopic monitoring. The flow rate of Mn(DPM)3 /THF solution was 0.2 sccm (Pr(DPM)3 /THF was 0.1 sccm, and Ca(DPM)2 /THF solution was varied 0.1-0.7 sccm. The optimal proportion of the flow rates of the liquid sources was determined by in situ infrared spectroscopic monitoring. The films were deposited at 480°C at 10 Torr pressure on Si(100) substrates having native SiO top layer. The deposited films (ca. 300nm thick) were annealed in flowing O2 at 600 C for 5 h.
The PCMO-based devices with top electrode
of Al or Ti exhibited nonlinear, asymmetric, and hysteretic I–V characteristics, the electric-pulse-induced resistance switching was observed; The resistance change was dependent on the Pr/Ca composition ratio of the PCMO films and the kind of the top
electrodes. The frequency response analysis suggested that the resistance switching in the PCMO-based devices was mainly due to the resistance change in the interface between the film and the electrode.Various resistance states for the multilevel data storage application were observed, depending on polarity and voltage of applied pulses. [[i] , [ii], [iii],[iv] ]
[i] T. Nakamura, K. Homma, T. Yakushiji, R. Tai, A. Nishio, K. Tachibana, Surf. Coat. Technology, 2007, vol 201, Iss 22–23, p.9275–9278, “Metalorganic chemical vapor deposition of metal oxide films exhibiting electric-pulse-induced resistance switching” http://www.sciencedirect.com/science/article/pii/S0257897207004859
[ii] T. Nakamura, K. Onogi, K. Homma, K. Tachibana, ECS Trans. 2009, vol. 25, iss.8, 865-869 doi: 10.1149/1.3207678, http://ecst.ecsdl.org/content/25/8/865.short
Resistive Switching in Metal Oxide Films Deposited by Metalorganic Chemical Vapor Deposition
[iii] T. Nakamura, K. Homma, R. Tai, A. Nishio, K. Tachibana, IEEE Transactions on Magnetics (Volume:43, Iss: 6), 2007, p.3070 – 3072, DOI: 10.1109/TMAG.2007.893115 “Electric-Pulse-Induced Resistance Switching in Magnetoresistive Manganite Films Grown by Metalorganic Chemical Vapor Deposition”, http://repository.kulib.kyoto-u.ac.jp/dspace/bitstream/2433/50172/1/04202857.pdf?origin=publication_detail
http://ieeexplore.ieee.org/xpl/login.jsp?tp=&arnumber=4202857&url=http%3A%2F%2Fieeexplore.ieee.org%2Fxpls%2Fabs_all.jsp%3Farnumber%3D4202857
[iv] T. Nakamura, R. Tai, K. Tachibana, Kunihide, J. Appl. Phys. 2006 (Vol:99, Issue: 8), 08Q302 - 08Q302-3, “Metalorganic chemical vapor deposition of magnetoresistive manganite films exhibiting electric-pulse-induced resistance change effect”
http://ieeexplore.ieee.org/xpl/login.jsp?tp=&arnumber=4951122&url=http%3A%2F%2Fieeexplore.ieee.org%2Fxpls%2Fabs_all.jsp%3Farnumber%3D4951122
Mn(thd)3 for (La,Pr,Ca)MnO3 by aerosol MOCVD
Mn(thd)3 , combined with La and Sr (or Ca) thd complexes, was used as precursor for the growth of high quality thin films of Ln1-xMx MnO3
on LaalO3 sustrates by aerosol MOCVD at 750 °C, followed by subsequent O2 annealing at 750 °C to stabilize the oxygen content of the films. The films had pseudocubic structure (XRD) with a lattice parameter linear in the average ionic radius of Ln
and M. The change of Ln1-xMxMnO 3 film morphology with increasing film thickness was studied. The morphological instability of the MOCVD process resulted in the formation of a hillocky surface with thickness >200 nm. The electrical properties of La 1-x
Ca x MnO 3 and La 1-x Sr x MnO 3 correlated with those reported for bulk and thin film materials. The substitution of Pr for La in La 1-x Sr x MnO 3 reduced the maximum resistivity temperature, Tp , non-linearly. La 0.35 Pr 0.35 Ca 0.3 MnO 3 /LaAlO 3 demonstrated
a very complex temperature dependence of the resistivity, described using a conceptual phase diagram of Ln 1-x M x MnO 3 . A marked GMR effect was observed for La 0.35 Pr 0.35 Ca 0.3 MnO 3 /LaAlO 3 below 21 K (ca. 10 10 %) and at ca. 70 K even in a field of
1 T. [[i]]
[i] O. Yu. Gorbenko, A. R. Kaul, N. A. Babushkina and L. M. Belova , J. Mater. Chem., 1997,7, 747-752, DOI: 10.1039/A606465E, “Giant magnetoresistive thin films of(La,Pr)0.7(Ca,Sr)0.3MnO3 prepared byaerosol MOCVD”, http://pubs.rsc.org/en/content/articlelanding/1997/jm/a606465e/unauth#!divAbstract
Mn(thd)3 for La1−xCaxMnO3, La1−xSrxMnO3 by MOCVD
Manganese tris(2,2,6,6-tetramethyl-3,5-heptanedionate) Mn(thd)3,
combined with La(thd)3, Sr(thd)2(H2O)2, Ca(thd)2, and Mn(thd)3, was applied for the growth of epitaxial perovskite La0.67Ca0.33MnO3 and La0.67Sr0.33MnO3 films (150 nm) by solid source CVD on LaAlO3 substrates and post annealed in O2 at 950 °C. The magnetic and electrical transport properties of the polycrystalline pellets, crystals, and annealed films were essentially the same. Below TC2 the intrinsic magnetization decreased as T2 (as expected
for itinerant electron ferromagnets) while the intrinsic resistivity increased proportional to T2. The constant and T2 coefficients of the resistivity were generally independent of magnetic field and alkaline earth element (Ca, Sr, or Ba). Hall effect measurements
indicated that holes were mobile carriers in the metallic state. Three distinct types of negative magnetoresistance were identified; the largest effect, observed near the Curie temperature, was 25% for the Sr and 250% [ΔR/R(H)] for the Ca compound. There
was also magnetoresistance associated with the net magnetization of polycrystalline samples which was not seen in films. A small magnetoresistance linear in H was observed even at low temperatures. The high temperature (above TC) resistivity of La0.67Ca0.33MnO3
was consistent with small polaron hopping conductivity with a slight transition at 750 K, while La0.67Sr0.33MnO3 did not exhibit activated conductivity until about 500 K, well above TC. The limiting low and high temperature resistivities placed a limit on
the maximum possible magnetoresistance of these materials, explaining why the "colossal" magnetoresistance correlates with the suppression of TC.[[i]]
[i] G. Jeffrey Snyder, Ron Hiskes, Steve DiCarolis, M. R. Beasley, T. H. Geballe, Phys. Rev. B 53, 1996, 14434 , DOI: http://dx.doi.org/10.1103/PhysRevB.53.14434
http://journals.aps.org/prb/abstract/10.1103/PhysRevB.53.14434, Intrinsic electrical transport and magnetic properties of La0.67Ca0.33MnO3 and La0.67Sr0.33MnO3 MOCVD thin films and bulk material
Mn(thd)3 for La1−xSrxMnO3 by MOCVD
Mn(thd)3 , in combination with La(thd)3 and Sr(thd)2 precursors, was used for the growth of polycrystalline La0.83Sr0.17MnO3 thin films on the lucalox substrates (99.9% polycrystalline Al2O3+0.1% MgO), which were used to obtain polycrystalline structures with naturally formed grain boundaries and crystallites whose dimensions were determined by film deposition temperature. The magnetoresistance of the grown films was studied in high pulsed magnetic fields up to 38 T in the temperature range 100–300 K, tt was found that the magnetoresistance was highest in the films having smallest crystallites. The main behaviour of high-field magnetoresistance was analysed using modified Mott’s hopping model assuming that the grain boundaries might be ferromagnetic with a Curie temperature T C being reduced in comparison with that of the crystallites interior.[[i]]
Tris(dipivaloylmethanato)manganese
[Mn(DPM)3], combined with [La(DPM)3] (and [Sr(DPM)2]), was applied for the growth of La1-xSrxMnOx manganite perovskite films by MOCVD. The behavior of the film precursors in the gas phase was studied using in situ infrared absorption spectroscopy under actual
chemical vapor deposition conditions. The temperature dependence of the infrared absorption indicated that Mn(DPM)3 (compared to La(DPM)3 and Sr(DPM)2) differed significantly in the decomposition temperature. The atomic composition of the deposited film was
controlled by the precursor densities obtained by the in situ spectroscopic measurements; such composition control by in situ monitoring technique is a mean to improve the reproducibility of the film magnetic properties.[[ii]]
[i] N. Žurauskienė, S. Balevičius, P. Cimmperman, V. Stankevič, S. Keršulis, J. Novickij, A. Abrutis, V. Plaušinaitienė, J. Low Temp. Phys., 2010, Vol. 159, Iss. 1-2, pp 64-67 “Colossal Magnetoresistance Properties of La0.83Sr0.17MnO3 Thin Films Grown by MOCVD on Lucalox Substrate”, http://link.springer.com/article/10.1007/s10909-009-0073-y#page-1
[ii] T. Nakamura, R. Tai, T. Nishimura, K. Tachibana, J. Appl. Phys. 2005, vol.97, Iss.10, p.10H712 - 10H712-3 , “Composition control of manganite perovskites in metalorganic chemical vapor deposition with in situ spectroscopic monitoring”
http://repository.kulib.kyoto-u.ac.jp/dspace/bitstream/2433/50173/1/JApplPhys_97_10H712.pdf
Mn(thd)3 for La1−x(Ca,Sr)xMnO3 by MOCVD
Mn(thd)3 precursor, dissolved in the organic solvent together with La(thd)3 and/or Sr(thd)2 or Ca(thd)2, was used as precursor for the growth
of La1–xAx(A = Ca or Sr)MnO3–δ thin films by liquid-delivery MOCVD on (001) MgO and (110)pseudo-cubic LaAlO3 substrates. The La1–xCaxMnO3–δ thin film on large lattice mismatched MgO exhibited very defective microstructures
(as determined by TEM), which consisted of two typical regions: the one close to the film–substrate interface had an epitaxial relationship to the substrate with many differently oriented domains nucleated on the substrate surface; the second consisted
of columnar grains with some degree of texture. In contrast, the smaller lattice-mismatched La1–xSrxMnO3–δ/(110)pseudo-cubic LaAlO3 film had good crystalline quality with highly oriented columnar grains but exhibited complicated dislocation
structures: misfit dislocations formed at the film–substrate interface, and two types of anomalous dislocations with limited contribution to relieving misfit stresses; the complicated dislocation configurations present in the sample were related to the
complex strain field in the film - the relative strains along the interface measured in the film were heterogeneous. The variations of the strains in the film were related to the local Curie temperature changes and second-order phase transitions of the film.[[i] ]
[i] Y. Xin, K. Han, N. Mateeva, H. Garmestani, P. N. Kalu, K-H. Dahmen, J. Mater. Res., 2001,vol.16, iss.11, p.3073-3083, “Microstructures of La1−xAx(A = Ca or Sr)MnO3−δ thin films by liquid-delivery metalorganic chemical vapor deposition”, http://lmm.gatech.edu/pdf/2001MicroThin-TEM.PDF
Mn(thd)3 for (La,Pr)1−x(Ca,Sr)xMnO3 by MOCVD
Mn(thd)3, combined with La(thd)3, Pr(thd)3, Ca(thd)2, Sr(thd)2, was applied for the growth of high quality (La,Pr)1−x(Ca,Sr)xMnO3
thin films by aerosol MOCVD at 750 °C, with subsequent annealing in O2 at 750 °C to stabilize the O content in the films.
The films were pseudocubic by XRD, with a lattice parameter changing linearly with the average ionic radius of Ln and M. The change of Ln 1-x M x MnO 3 film morphology with increasing film thickness was studied; for thickness >2000 Å a hillocky surface
was obtained. The substitution of Pr for La in La1-xSrxMnO3 non-linearly reduced the maximum resistivity temperature Tp,. La0.35 Pr 0.35Ca 0.3 MnO 3 /LaAlO3 demonstrated a complex
temperature dependence of the resistivity. La0.35Pr0.35Ca 0.3 MnO3 /LaAlO 3 demonstrated a marked GMR effect below 21 K (ca. 10 10 %) and at ca. 70 K even in a field of 1 T.[[i]]
[i] O.Yu. Gorbenko, A.R. Kaul, N.A. Babushkina, L.M. Belova, J. Mater. Chem., 1997, 7, 747-752, DOI: 10.1039/A606465E, “Giant magnetoresistive thin films of (La,Pr)0.7(Ca,Sr)0.3MnO3 prepared by aerosol MOCVD”,http://pubs.rsc.org/en/content/articlelanding/1997/jm/a606465e/unauth#!divAbstract
Mn(thd)3 for Nd1−x(Ca,Sr)xMnO3 by MOCVD
Mn(thd)3, in combination with Nd (or Pr,La) and Ca, Sr thd complexes were applied for the growth of thin epitaxial films of complex oxide materials including CMR manganites R1-xAxMnO3 (R = La, Pr, Nd ; A = Ca, Sr) by aerosol and flash MOCVD. Raman spectrometry was found to be the only non-destructive way of control of the oxygen content of the layers (including the analysis of the oxygen isotope content) and the appearance of secondary phases. Raman spectrometry was applied to the analysis of perovskite thin films with only minor deviations from a cubic symmetry, what allowed to measure delicate variations of the structure with the composition of thin film perovskite-like solid solutions.[[i][PS1] ]
[i] B. Güttler, O.Yu. Gorbenko, M.A. Novozhilov, S.V. Samoilenkov, V.A. Amelichev, G. Wahl, H.W. Zandbergen, Proc. Twelfth European Conf. Chem. Vap. Dep., J. Phys. IV France 09 (1999) Pr8-1179-Pr8-1186, DOI: 10.1051/jp4:19998147
http://jp4.journaldephysique.org/articles/jp4/abs/1999/08/jp4199909PR8147/jp4199909PR8147.html Application of Raman spectrometry for the characterization of complex oxide thin films grown by MOCVD
Mn(thd)3 for (La,Pr)1−xNaxMnO3 films grown by MOCVD
Mn(thd)3, combined with Na(thd), La(thd)3, Pr(thd)3 or Nd(thd)3 was applied for the growth of the solid solutions including (La,R)l-xNaxMnO3 (R = Pr, Nd) on the
single crystalline substrates (single crystalline (001) MgO, (001) ZrO2(Y2O3), (001) LaAlO3, (001) SrTiO3) by aerosol MOCVD, characterized by XRD and HREM. The single source MOCVD allowed the reproducible preparation of the 3-4 metal perovskite manganate The growth of the epitaxial heterostructures including CMR manganates was demonstrated.[[i] , [ii]]
[i] O.Yu. Gorbenko, I.E. Graboy, A.A. Bosak, V.A. Amelichev, A.Yu. Ganin, A.R. Kaul, G. Wahl, H.W. Zandberben , J. Phys. IV France 09 (1999) Pr8-659-Pr8-666, DOI: 10.1051/jp4:1999883, “Chemical composition effects in the thin films of the colossal magnetoresistive perovskite manganates grown by MOCVD”, http://jp4.journaldephysique.org/articles/jp4/abs/1999/08/jp4199909PR883/jp4199909PR883.html
[ii] O.Yu Gorbenko, I.E Graboy, A.R Kaul, H.W Zandbergen, J. Magnetism Magnetic Mater., 2000, Vol. 211, Iss 1–3, p.97–104 , “HREM and XRD characterization of epitaxial perovskite manganites”,
www.researchgate.net/publication/235693665_HREM_and_XRD_characterization_of_epitaxial_perovskite_manganites/file/60b7d52d0572256c9d.pdf
Manganese tris(2,2,6,6-tetramethyl-2-sila-3,5-heptanedionate) Mn(tBuCOCHCOSiMe3)3, (2–sila analogue of Mn(thd)3) ,
Manganese tris(2,2,6,6-tetramethyl-2-sila-3,5-heptanedionate) Mn(tBuCOCHCOSiMe3)3, (the 2–sila analogue of Mn(thd)3) , was synthesized by the reaction of MnCl2 (dissolved in aqueous ethanol) and sodium 2,2,6,6-tetramethyl-2-sila-3,5-heptanedionate formed in situ by reaction of sodium hydroxide and H-silaTHD ligand (both ethanol solutions); the resulted green dark solution was evaporated and after extraction with pentane the crude Mn(tBuCOCHCOSiMe3)3 was sublimed yielding an analytically pure metal complex.
The volatility of the complex (T.sub.50% = 119°C) allows to potentially
use it as manganese precursor for MOCVD applications.[[i],[ii]]
[i] K. K. Banger, R. Claessen, A. E. Kaloyeros, A. Kornilov, P.J. Toscano, J.T. Welch, US Patent US 6099903 A, 2000, “MOCVD processes using precursors based on organometalloid ligands”, http://www.google.com/patents/US6099903
[ii] J. T. Welch, P. J. Toscano, R. Claessen, A. Kornilov, K. Kumar Banger, US 6359159 B1, “MOCVD precursors based on organometalloid ligands” http://www.google.com/patents/US6359159
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