Manganese (I) alkylcyclopentadienyls tris(carbonyls)
Manganese cyclopentadienyl-tricarbonyl (cymantrene) MnCp(CO)3 , as well as its methylated analogue manganese methylcyclopentadienyl-tricarbonyl Mn(MeCp)(CO)3 (methycymantrene), have been applied as MOCVD precursor of Mn-containing layers.
Both MnCp(CO)3 and Mn(MeCp)(CO)3 are thermally stable, relatively volatile liquids or low melting solids. The pyrolysis
mechanism of cymantrene MnCp(CO)3 as well as its methylated analogue cymantrene was studied in [[i]].
[i] Douglas K. Russell , Iain M. T. Davidson , Andrew M. Ellis , Graham P. Mills , Mark Pennington , Ian M. Povey , J. Barrie Raynor , Sinan Saydam , Andrew D. Workman, Organometallics, 1995, 14 (8), pp 3717–3723, DOI: 10.1021/om00008a019, http://pubs.acs.org/doi/abs/10.1021/om00008a019, “ Mechanisms of Pyrolysis of Tricarbonylcyclopentadienylmanganese and Tricarbonyl(methylcyclopentadienyl)manganese"
MnCp(CO)3 for (Pr,Ca)MnO3 films by MOCVD
Mn(C5H5)(CO)3, in combination with Pr(OCH(CH3)2)3, and Ca(tmhd)2, has been applied as Mn precursor for the growth of (Pr,Ca)MnO3 films by liquid
injection MOCVD. The solid precursors were dissolved in a mixed solvent of butyl ether and tetraglyme, and the resulting liquid precursor solution was injected into a vaporizer and transported into the MOCVD chamber.
Molecular oxygen O2 is used as O-source, it is also introduced into the MOCVD chamber, where the precursor vapor and O2 react to form a (Pr,Ca)MnO3 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, "
MnCp(CO)3 for Mn-doped ZnS films by MOCVD
Tricarbonylmethylcyclopentadienyl manganese (TCM) Mn(C5H5)(CO)3 has been applied as Mn dopant source for the ZnS:Mn thin-film
emitting layer in the insulating ceramic-type thin-film EL (ICTFEL) devices. The influence of Mn doping conditions on the electroluminescent (EL) characteristics was studied. An ICTFEL device with an emitting layer
doped with Mn(C5H5)(CO)3 represented a high luminance of 9300 cd/m2 at applied voltage of 300 V. Mn(C5H5)(CO)3 was demonstrated to be an excellent
manganese source for the growth on Mn-doped MOCVD method, and the optimum content of Mn is ~1.3%.[[i]]
[i] T. Miyata, T. Minami, S. Takata, J. Cryst. Growth, Vol. 117, Iss. 1–4, 1992, p.1021–1025
http://www.sciencedirect.com/science/article/pii/002202489290905X ,“Influence of Mn doping conditions on electroluminescent characteristics of ZnS:Mn thin-film electroluminescent (TFEL) devices using insulating ceramic”
MnCp(CO)3 for GaMnN films by MOCVD
Cyclopentadienyl manganese tricarbonyl (Cp2MnT) Mn(C5H5)(CO)3 has
been applied manganese source for the growth of GaMnN thin films by plasma-assisted MOCVD on c-plane sapphire substrates at growth temperature 625-700°C and molar V/III ratios 440-1080. The growth rate and Mn incorporation into GaN highly depended on growth
parameters. Thus, the highest Mn incorporation (6.4 %) into single phase GaMnN (0002) was obtained at growth temperature of 650°C. However, at growth temperature of 700°C, the maximum of Mn incorporation into GaMnN films still allowing to get single
phase film was 3.2 %. High growth temperatures tended to improve the surface morphology of GaMnN, according to AFM. The magnetization measurements demonstrated that hysteresis behavior at room temperature depended on the Mn concentration, with coercivity,
saturation and remnant magnetization values being in the range of 350-800 Oe, 20-39 emu/cm3 and 10.2-34.4 emu/cm3, respectively. For the GaMnN films grown at 650 °C, the highest magnetic moment per Mn-atom was obtained for Mn concentration of 2.0 %, i.e.
3.1 μB/Mn-atom; whereas for the films grown at 700°C, the highest magnetic moment per Mn-atom 3.7 μB /Mn-atom was obtained for 2.5 % Mn concentration. [[i]]
[i]Mulyanti, B. ; Arifin, P., Semiconductor Electronics (ICSE), 2010 IEEE International Conference on, p. 56-59, DOI : 10.1109/SMELEC.2010.5549459
http://ieeexplore.ieee.org/xpl/login.jsp?tp=&arnumber=5549459&url=http%3A%2F%2Fieeexplore.ieee.org%2Fxpls%2Fabs_all.jsp%3Farnumber%3D5549459, “Plasma-assisted MOCVD growth of GaMnN”
MnCp(CO)3 for GaN:Mn doped films by MOCVD
Cyclopentadienyl manganese tricarbonyl (CpMnTc) Mn(C5H5)(CO)3 has been applied as Mn precursor (in combination with trimethylgallium (TMGa) and nitrogen (N2) as of Ga, N sources) for the growh of GaN:Mn thin films by plasma-assisted MOCVD, at deposition temperatures 625 to 700 C, V/III flux ratio 440 to 1080 , Mn/Ga molar fraction 0.2 to 0.5, the deposition
pressure was 0.7 Torr, growth time 2 h, resuling in the 300-500 nm thickness of the films.. The deposited layers were characterized by EDX and XRD to analyze atomic composition and crystal structure of the grown films, respectively; the surface morphology
was studied by AFM and SEM. The effect of Mn incorporation into GaN:Mn thin films on their structural properties, surface morphology and magnetic properties was investigated. The decrease in lattice constant accompanied by the increase in FWHM is due to incorporation
of substitutional Mn on the Ga sub-lattice. The maximum Mn concentration that still produced single phase GaN:Mn (0002) depended on growth temperature (up to 6.6% Mn was achieved). The highest concentration of Mn atoms incorporated in the wurtzite structure
substitutionally was 2.5%. Above this concentration, part of Mn atoms was incorporated into GaN matrix interstitially. The films with 6.4% of Mn has a better surface morphology than that with 6.6 % of Mn, according to AFM. Magnetization measurements demonstrated
hysteresis behavior at room temperature. The maximum of magnetic moment was achieved by the film with Mn concentration of 2.5 %. [[i] , [ii] , [iii]]
[i]Study of Mn Incorporation Into GaN:Mn Magnetic Semiconductor Thin Films Prepared by Plasma Assisted MOCVD, Mulyanti, B., Subagio, A. ; Sutanto, H.; Arsyad, F.S. ; Arifin, P.; Budiman, M.; Barmawi, M., Nanoscience and Nanotechnology, 2006. ICONN '06. Intern. Conf. on., 3-7 July 2006, Digital Object Identifier : 10.1109/ICONN.2006.340622
http://ieeexplore.ieee.org/xpl/articleDetails.jsp?tp=&arnumber=4143402&url=http%3A%2F%2Fieeexplore.ieee.org%2Fxpls%2Fabs_all.jsp%3Farnumber%3D4143402
[ii] Budi Mulyanti, A. Subagio, F. S. Arsyad, P. Arifin, M. Barmawi, Irzaman Irzaman, Z. Jamal, U. Hashim, J. Mathem. Fundam. Sci., Institut Teknologi Bandung, ITB J. Sci ., Vol 40, No 2 (2008) , p.97-108, http://journals.itb.ac.id/index.php/jmfs/article/view/36/32
http://journals.itb.ac.id/index.php/jmfs/article/view/36, “Effect of Growth Temperature and Mn Incorporation on GaN:Mn Thin Films Grown by Plasma-Assisted MOCVD”
[iii] B Mulyanti, A Subagio, H Sutanto, Proceeding of Asian Physics Symp., 2005, Bandung, Indonesia, “Temperature Dependence of Mn incorporation into GaN: Mn Deposited Using PA-MOCVD”
Manganese methylcyclopentadienyl-tricarbonyl Mn(MeCp)(CO)3 (methylcymantrene)
Manganese methylcyclopentadienyl-tricarbonyl Mn(MeCp)(CO)3 (methylcymantrene) is thermally stable, relatively volatile liquid (is liquid at 17 °C, having 40 Pa vapor pressure). The dependence of Mn(MeCp)(CO)3 (TCMn) vapour pressure versus evaporation temperature was presented in [[i]] (see Fig.). The pyrolysis mechanism of methylcymantrene MnCp(CO)3 was studied in [[ii]].Mn(MeCp)(CO)3 has been applied as MOCVD precursor for the growth of Mn-containing layers.
[i] Chen Zhi-Tao et al 2006 Chinese Phys. Lett. 23 1286,
cpl.iphy.ac.cn/EN/article/downloadArticleFile.do?attachType=PDF&id=40876
[ii] Douglas K. Russell , Iain M. T. Davidson , Andrew M. Ellis , Graham P. Mills , Mark Pennington , Ian M. Povey , J. Barrie Raynor , Sinan Saydam , Andrew D. Workman, Organometallics, 1995, 14 (8), pp 3717–3723, DOI: 10.1021/om00008a019, http://pubs.acs.org/doi/abs/10.1021/om00008a019, “ Mechanisms of Pyrolysis of Tricarbonylcyclopentadienylmanganese and Tricarbonyl(methylcyclopentadienyl)manganese
Mn(MeCp)(CO)3 for Mn silicate (MnSiOx), Mn silicide (MnSix) films by MOCVD
Methylcyclopentadienylmanganese tricarbonyl Mn(MeCp)(CO)3 has been applied as Mn precursor for the MOCVD growth of Mn-containing layers on Si/SiO2 substrates. It was found by XPS studied
that manganese silicate MnSiOx layer grows upon reaction with the top SiO2 surface at the temperatures typically used for deposition (ca. 550-750 K), and a thin manganese slicicide MnSix film develops lter at the SiO2/Si(100) interface. [[i]]
[i] Huaxing Sun, Xiangdong Qin, Francisco Zaera, J. Phys. Chem. Lett., 2011, 2 (20), p.2525, DOI: 10.1021/jz201177w, http://pubs.acs.org/doi/abs/10.1021/jz201177w, "Chemical Nature of the Thin Films that Form on SiO2/Si(100) Surfaces Upon Manganese Deposition”
Mn(MeCp)(CO)3 for metal Mn by MOCVD on Si/SiO2
Manganese (I) methylcyclopentadienyl Mn(MeCp)(CO)3 (and in comparison Mn(N,N’-diisopropylpentylamidinate)2) has been tested as MOCVD precursor for the growth of
Mn silicate and metal Mn films on Si/SiOx substrates. Mn(MeCp)(CO)3 proved quite unreactive as MOCVD precursor (compared to Mn(N,N’-diisopropylpentylamidinate)2) ), despite use of recently developed electron-impact gas-phase preactivation step. Slow
deposition rates were observed with Mn(MeCp)(CO)3, being slower at higher temperature because of an unfavorable kinetic competition with Mn diffusion into the bulk. For both precursors, a nonstoichiometric mixture of MnOx + SiOx and Mn silicate is formed on
the surface first, possibly followed by the formation of a thin subsurface Mn silicide layer. Metallic Mn(0) films have been grown on top of the resulting Mn silicate/Mn silicide structure which acts as an effective diffusion barrier. [[i]]
[i]Huaxing Sun, Francisco Zaera, J. Phys. Chem. C, 2012, 116 (44), p.23585, DOI:10.1021/jp309083a,http://pubs.acs.org/doi/abs/10.1021/jp309083a, “ Chemical Vapor Deposition of Manganese Metallic Films on Silicon Oxide Substrates”
Mn(MeCp)(CO)3 for metal Mn by MOCVD on GaAs
Tricarbonyl (methylcyclopentadienyl) manganese (TCMn) Mn(MeCp)(CO)3 has been successful applied as precursor for MOCVD of metal manganese Mn films on GaAs(100) and GaAs(111)
substrates; the onset of diffusion limited growth occurred at ~470 °C temperature. Over this transition temperature, the growth was nearly independent of the temperature and was limited only by the precursor diffusion rate to the substrate. At low temperatures,
the growth rate was limited by Mn(MeCp)(CO)3 pyrolysis behaviour and was thermally activated with 220 kJ mol−1activation energy. The activation energy obtained for the decomposition of the TCMn was 236 kJ mol−1. No growth of Mn films took place
below 410 °C; the morphology of the layers grown at the higher temperature of 470 °C was significantly better than for layers grown at lower temperatures. Ex-situ RHEED measurements showed the films were polycrystalline Mn lqayers having good surface
morphology. Mn film surface roughness was ~ 4 nm and was probably limited by oxidation, when exposed to air.[[i]]
[i]S. Wen-bin, K.Durose, A.W.Brinkman, B.K.Tanner, Mater.Chem.Phys., Vol.47, Iss.1, 1997, p.75, http://www.sciencedirect.com/science/article/pii/S0254058497800314 , ”Growth and characterization of magnetic metal Mn film by MOCVD”
Mn(MeCp)(CO)3 for Mn-doped ZnS phosphors by MOCVD
Tricarbonyl methylcyclopentadienyl manganese Mn(MeCp)(CO)3 was applied as manganese source for Mn-doping of ZnS-based phosphor by MOCVD. The growth was carried out in a quartz
reactor at 375°C deposition temperature and 35 kPa pressure; besides Mn(MeCp)(CO)3 as Mn source, diethylzinc ZnEt2 and carbon disulphide CS2 as the Zn and S source materials were applied. [[i]]
[i] Oxide phosphors as thin-film electroluminescent materials, T. Minami ; H. Yamada ; Y. Kubota ; T. Miyata , Far East and …, 1997 –Proc. SPIE 3242, Smart Electronics and MEMS, 229 (1997); doi:10.1117/12.293564; http://dx.doi.org/10.1117/12.293564, http://proceedings.spiedigitallibrary.org/proceeding.aspx?articleid=933359.
Mn(MeCp)(CO)3 for YMnO3 films by MOCVD
Manganese tricarbonyl methylcyclopentadienyl Mn(MeCp)(CO)3, in combination with Y(thd)3 as Y source and O2 as oxidizer, has been applied a precursor for
the MOCVD growth of ferroelectric perovskite YMnO3 thin films on Si and GaAs substrates at 500°C deposition temperature and growth pressure 2-10 Torr. The evaporation temperature of Mn(MeCp)(CO)3 was 160-180°C,
Mn(MeCp)(CO)3 carrier gas 5-10 sccm N2 (plus 20-40sccm for N2), dilute gas/oxidiser 500-1000 sccm O2. In these conditions growth rate of YMnO2 films was 10-20 nm/min (0.6-1.2µ/h). The deposited YMnO3 films had excellent film uniformity, composition control,
high density, and excellent step coverage. [[i]]
[i] S.B. Desu, Ch.-H. Peng,J.Si,US5625587 A, 1997, www.google.com/patents/US5625587 , “Rare earth manganate films made by metalorganic decomposition or metalorganic chemical vapor deposition for nonvolatile memory devices”
Mn(MeCp)(CO)3 for (Pr,Ca)MnO3 films by MOCVD
Manganese methylcyclopentadienyl tris(carbonyl) Mn(CH3C5H4)(CO)3, in combination with
Pr(tmhd)3, and Ca(tmhd)2 and O2 as oxider, was dissolved in a mixed solvent of butyl ether and tetraglyme, and applied for the growth of (Pr,Ca)MnO3 films by MOCVD.[[i]]
[i]WW.Zhuang, ST.Hsu, W.Pan, US Patent 6,887,523, 2005, www.google.com/patents/US6887523 “Method for metal oxide thin film deposition via MOCVD”
Mn(MeCp)(CO)3 for MnAs by MOCVD
Tricarbonylmethylcyclopentadienyl manganese (TCM) Mn(MeCp)(CO)3, in combination with arsine AsH3, has been applied for the growth of ferromagnetic manganese arsenide (MnAs) thin films by
atmospheric pressure MOCVD. A detailed study of the MnAs growth characteristics and resulting magnetic and structural properties.was presented [[i]].
[i] P.A. Lane, B. Cockayne, P.J. Wright, P.E. Oliver, M.E.G. Tilsley, N.A. Smith, I.R. Harris, J. Cryst. Growth, Vol 143, Iss 3–4, 2 Oct1994, Pages 237–242, http://www.sciencedirect.com/science/article/pii/0022024894900620 , “Metalorganic chemical vapour deposition of manganese arsenide for thin film magnetic applications”
Mn(MeCp)(CO)3 for Ga1-xMnxN films grown by MOCVD
Tricarbonyl (methycyclopentadienyl) manganese ((MCP)2Mn) Mn(MeCp)(CO)3 has been applied as Mn dopant source for the growth of Ga1−xMnxN epitaxial films by MOCVD. Magnetic measurements indicated n-type conductivity (x=0.01) and ferromagnetic ordering with Curie temperature above RT in the deposited films,. The magnetic moment per Mn atom decreased for Mn concentration changing from 0.01 to 0.03. Magneto-transport properties were performed in the temperature range of 2–300 K; the magneto-resistance (MR) changed from negative to positive effect with increasing temperature. The negative MR effect at low temperature was explained by reduction of the magnetic scattering of the Mn ions under the applied magnetic field. Furthermore, the zero-field-cooled (ZFC)/field-cooled (FC) and MR behavior at low temperature confirmed that the ferromagnetism and paramagnetism coexisted in Ga1−xMnxN films.[[i]]
A series of (Ga, Mn)N samples with varying Mn concentrations were investigated Raman spectra, a new vibrational mode at 577 cm−1 obtained was assigned to the local vibrational mode (LVM) of Mn substituting the Ga site, whereas another mode at 667 cm−1 arised from vibrational mode of nitrogen vacancies-related defects. Mn doping increased the lattice disorder and other built-in defects such as the nitrogen vacancies. The room temperature ferromagnetism was not only dependent on the substitutional Mn content but also strongly related to these lattice disorder and negative defects in (Ga, Mn)N films. [[ii] ]
Tricarbonyl (methylcyclopentadienyl) manganese (TCMn) Mn(MeCp)(CO)3
was applied as Mn source during growth of epitaxial films of Ga½xMnxN on c-sapphire substrates by low-pressure MOVPE un a horizontal pressure-controllable MOCVD reactor with rf heating. The Ga½xMnxN epilayers samples showed ferromagnetic behaviour
up to a temperature of T = 380K with hysteresis curves showing a coercivity of 50-100 Oe. No ferromagnetic second phases and no significant deterioration in crystal quality with Mn incorporation was detected by high-resolution XRD. According to x-ray absorption
near-edge structures measurements, Mn atoms substituted Ga atoms. The Mn concentration reaching x = 0.038 was determined by proton-induced x-ray emission.[[iii]]
[i] Xuelin Yang, Zhitao Chen, Jiejun Wu, Yaobo Pan, Yan Zhang, Zhijian Yang, Tongjun Yu, Guoyi Zhang, Journal of Crystal Growth, Vol 305, Issue 1, 1 July 2007, Pages 144–148, http://www.sciencedirect.com/science/article/pii/S0022024807004307 Magnetic and magneto-transport properties of Ga1−xMnxN grown by MOCVD
[ii]Xuelin Yang, Jiejun Wu, Zhitao Chen, Yaobo Pan, Yan Zhang, Zhijian Yang, Tongjun Yu, Guoyi Zhang, Solid State Communications, Vol 143, Issues 4–5, July 2007, Pages 236–239, http://www.sciencedirect.com/science/article/pii/S003810, 9807003833 “Raman scattering and ferromagnetism of (Ga, Mn)N films grown by MOCVD”
[iii] Chen Zhi-Tao, Su Yue-Yong, Yang Zhi-Jian, Zhang Yan, Zhang Bin, Guo Li-Ping, Xu Ke, Pan Yao-Bao, Zhang Han, Zhang Guo-Yi, Chinese Phys. Lett. 2006, 23 1286 doi:10.1088/0256-307X/23/5/061, http://iopscience.iop.org/0256-307X/23/5/061
cpl.iphy.ac.cn/EN/article/downloadArticleFile.do?attachType=PDF&id=40876
Room-Temperature Ferromagnetism of Ga1?xMnxN Grown by Low-Pressure Metalorganic Chemical Vapour Deposition
Mn(MeCp)(CO)3 for Zn1-xMnxO films grown by MOCVD
Tricarbonyl methylcyclopentadienyl manganese (TCMn) Mn(MeCp)(CO)3 (liquid at 17 °C, having 40 Pa vapor pressure), in combination with Diethyl-zinc (DEZn), and tertiary-butanol (tBu) as Zn and O sources, has been applied as Mn precursor for the MOCVD growth of single-phase thin films of the diluted magnetic semiconductor Zn1−xMnxO at 450 °C on fused silica and (0 0 0 1) sapphire substrates. Zn1−xMnxO layers on silica were polycrystalline with [0 0 1] preferential orientation, whereas Zn1−xMnxO films on c-sapphire were (0 0 0 1) epitaxial with 30° rotation of the Zn1−xMnxO [1 0 0] direction with respect to the [1 0 0] of the substrate. The Mn content varied in the 0–30% range and was always higher in samples grown on sapphire substrates under the same conditions. Manganese incorporated as substitutional Mn2+ ions, as was found from variations of a and c lattice parameters (determined by XRD) following Vegard's law, as well as decrease of electron mobility with increasing incorporation of Mn in ZnO as per Hall effect measurements, and optical transmission measurements showing shift of the absorption edge towards higher energies.[[i]]
Increase of Mn incorporation resulted in opening of the band gap, observed as a blue shift in energy regarding pure ZnO [[ii] ]
Thermal annealing of MOCVD grown Zn1–xMnxO layers between
300 °C and 1000 °C in an O2 atmosphere modified both their lattice parameters and their magnetic properties. Combined XRD and EPR studies indicated a redistribution of intrinsic defects but persistent antiferromagnetic phase in the annealed films [[iii] , [iv]]
[i]E. Chikoidze, Y. Dumont, F. Jomard, D. Ballutaud, P. Galtier, D. Ferrand, V. Sallet, O. Gorochov, Materials Research Bulletin, Vol 41, Issue 6, 2006, p. 1038–1044 Growth of the Zn1−xMnxO alloy by the MOCVD technique
[ii] E. Chikoidze, Y. Dumont, F. Jomard, O. Gorochov, “Thin Solid Films, Vol. 515, Iss.24, 2007, p.8519–8523, First International Symposium on Transparent Conducting Oxides
http://www.sciencedirect.com/science/article/pii/S0040609007004695
Electrical and optical properties of ZnO:Mn thin films grown by MOCVD
[iii] E. Chikoidze, H. J. von Bardeleben, Y. Dumont, F. Jomard, O. Gorochov
physica status solidi (c), Volume 3, Issue 4, pages 1001–1004, March 2006
http://onlinelibrary.wiley.com/doi/10.1002/pssc.200564651/abstract , “Influence of annealing on the structural and magnetic properties of epitaxial Zn1–xMnxO films grown by MOCVD on sapphire”
[iv] E. Chikoidze, Y. Dumont, H.J. von Bardeleben, J. Gleize, O. Gorochova, Journal of Magnetism and Magnetic Materials, Vol 316, Iss 2, Sep 2007, p. e181–e184
http://www.sciencedirect.com/science/article/pii/S0304885307001874
Effect of oxygen annealing on the Mn2+ properties in ZnMnO Films
Mn(MeCp)(CO)3 for Mn-doped ZnS by MOCVD
Thermally stable tricarbonylmethylcyclopentadienyl manganese Mn(MeCp)(CO)3 has been applied as Mn dopant (with an aid of plasma-enhanced decomposition) for the growth of fluorescent ZnS: Mn layers by MOCVD. The Mn concentration in the deposited layers (~1 wt%) was growth temperature-independent, indicating that the Mn dopant was completely decomposed by plasma and effectively incorporated in the layers. [[i] ]
Tricarbonyl-(methylcyclopentadienyl)-manganese (TCPMn) Mn(MeCp)(CO)3 was applied as Mn precursor for the growth of Mn-doped ZnS phosphor thin films (in combination with diethylzinc as Zn source) by low-pressure MOCVD used in the alternating-current thin film electroluminescent devices (TFELDs). A temperature and flow modulation (TFM) technique was developed to modulate the Mn doping profile in grown ZnS phosphor material (which includes modulation of both substrate temperature and flows of MO sources). A structure consisting of alternating layers of undoped ZnS grown at 400°C and Mn-doped ZnS with Mn incorporated into the undoped ZnS at 550°C were prepared by TFM technique, According to XRD, MnSx phases were present within the ZnS host crystal matrix for the modulation doped samples, while a MnxZn1-xS solid solution was present in the uniformly doped samples. The luminescence efficiency of the TFELDs could be modified by growing the phosphor with dopant (luminescent center) modulation: thus, the TFELDs with a single modulated doping phosphor layer demonstrated lower threshold voltages in the range 70 to 80 V with light emission at 580-587 nm wavelengths, whereas twofold increase in the total thickness of the undoped ZnS layer, increased by a factor of 20 the brightness and x10 the luminescence efficiency (measured at threshold voltage plus 40 V). Electroluminescent (EL) characteristics had higher luminescence efficiency for the phosphors grown with multiple dopant layers [[ii] ]
Use of Mn(MeCp)(CO)3 (TCM) was mentioned to be useful for the MOCVD growth of Mn-doped ZnS layers (grown using ZnMe2 and H2S as Zn and S sources, and H2 carrier gas). Thus, Hirabuyashi and Kozanaguchi obtained very high luminance ZnS:Mn electroluminescent devices by using Mn(MeCp)(CO)3 as dopant gas (>5000 cd/m2 operated at 5kHz and 130V). The disadvantage of Mn(MeCp)(CO)3 as Mn doping precursor is that >450°C temperatures have to be used to achieve efficient doping, but this high temperature results in reaction between conducting ZnS:Mn and conducing ITO ((In,Sn)O) layer.[[iii] ,[iv]] ]
Tricarbonylmethyl cyclopentadienyl manganese (TCM) Mn(MeCp)(CO)3 was mentioned to be useful as Mn dopant precursor of the ZnS film ; the obtained ZnS:Mn films were applied for the TFEL device fabrication [[v] ]
Tricarbonylmethyl cyclopentadienyl manganese (TCM) Mn(MeCp)(CO)3 dissolved in decaline (5% solution), has been applied as Mn source for the MOCVD deposition of TFEL stacks contaning ZnS:Mn layers (with zinc diethyldithiocarbamate
as Zn source). The Mn bearing vapor was introduced to reactor by exposure of Mn(MeCp)(CO)3 solution to the reduced pressure via a series of needle valves (whereas Zn precursor was evaporated as solid at 160-200°C and introduced using N2 carrier via a calibrated
needle valve). Substrate temperature was 400°C, total system pressure up to 25 mbar, obtained growth rates of ZnS:Mn was ~0.15 µm/h. Optical badgap measurements indicated that grown ZnS-Mn films had hexaconal structure (Eg(meas) 3.60eV - close to Eg(hex) 3.56 eV, while for cubic modification E g=3.80eV), a high degree of preferred orientation was indicated by the single sharp (002) peak found by XRD measurements. [[vi] ]
[i] T. Yasuda, K. Hara, M. Mizuta, H. Kukimoto, J. Cryst. Growth, vol.96, Iss4, 1989, p.979, http://www.sciencedirect.com/science/article/pii/0022024889906593
Plasma-enhanced doping of manganese in zinc sulfide layers during metalorganic chemical vapor deposition
[ii] J. E. Yu, K. S. Jones, P. H. Holloway, B. Pathangey, E. Bretschneider, T. J. Anderson, S. S. Sun, C. N. King
J. Electronic Materials, March 1994, Volume 23, Issue 3, pp 299-305
http://link.springer.com/article/10.1007/BF02670639#page-1 , “Temperature and flow modulation doping of manganese in ZnS electroluminescent films by low pressure metalorganic chemical vapor deposition
[iii] C Yang, Master’s .Thesis 1994
http://scholarworks.sjsu.edu/cgi/viewcontent.cgi?article=1880&context=etd_theses
“Study of the degradation mechanisms and lifetime optimization of thin film ZnS electroluminescent devices made by MOCVD” and refs therein.
[iv] William H. Perez, Master's Theses and Graduate Research1992, San Jose State University, http://scholarworks.sjsu.edu/cgi/viewcontent.cgi?article=1490&context=etd_theses&sei-redir=1&referer=http%3A%2F%2Fscholar.google.de%2Fscholar%3Fstart%3D80%26q%3Dmangase%2 , “Growth of polycrystalline ZnS by MOCVD using thiophene as a sulfur source”
[v] A Saunders, A Vecht, Electroluminescence, Springer Proceedings in Physics Volume 38, 1989, pp 210-217 http://link.springer.com/chapter/10.1007/978-3-642-93430-8_45#page-1 , “The role of chemical vapour deposition in the fabrication of high field electroluminescent displays”
[vi] D.C. Morton, M.R. Miller, A.Vecht, A. Saunders, G. Tyrell, E.Hryckowian, R.J. Zeto, L. Calderon, R.T.Lareau, Electroluminescence, Springer Proc. Phys., vol.38, 1989, pp 228
Mn(MeCp)(CO)3 for Mn-doped ZnSe by MOCVD
Tricarbonylmethylcyclopentadienyl manganese Mn(MeCp)(CO)3 has been successfully applied as Mn dopant to dope ZnSe thin films grown by organometallic chemical vapour deposition. The concentration of manganese in ZnSe:Mn layers was studied as a function of growth conditions; its distribution across the films was determined by SIMS. The efficiency of Mn as a luminescence activator in grown ZnSe:Mn films has been studied by cathodoluminescence and electroluminescence measurements.[[i]]
Methylcyclopentadienyl tricarbonyl manganese Mn(MeCp)(CO)3 was mentioned to be applicable as manganese dopant precursor for the growth of solid solution of wide gap semiconductor material Zn1-xMnxSe by MOCVD at 400-550°C, however, the concentration of Mn in the solid solution was mentioned to be limited to 0.1% by low volatility of Mn precursor.[[ii] ]
Methylcyclopentadienyl manganese tricarbonyl Mn(MeCp)(CO)3) (Alfa Products Ltd) has been applied as Mn precursor for the growth of Znl-xMnxSe (x-0.01) epitaxial layers on GaAs by atmospheric pressure MOCVD (ZnMe2 and 10% H2Se in H2 were applied as
Zn and Se sources). The deposited Zn1-xMnxSe (x approximately=0.01) epitaxial layers were characterized by photoluminescence measurements at 2 K: the dominant feature was the I2 emission due to excitons bound at neutral donors (D0X). When magnetic fields of
several tesla are applied, the emission shifted to lower energy and increased dramatically in intensity, in a way similar to Cd1-xMnxSe and Cd1-xMnxTe. The changes were explained by the exchange enhancement of the magnetic field being sufficient for the lowest
energy level of the free exciton to sweep across the D0X levels, so that the bound exciton becomes destabilised. [[iii]]
[i] P.J. Wright, B.Cockayne, A.F. Cattell, P.J. Dean, A.D. Pitt, J. Cryst. Growth,Vol.59, Iss.1–2, 1982, p.155–160, Proceedings of the International Conference on II-VI Compounds
http://www.sciencedirect.com/science/article/pii/0022024882903177
“Manganese doping of ZnS and ZnSe epitaxial layers grown by organometallic chemical vapour deposition”
[ii] B. Cockayne, P. J. Wright , Growth and Optical Properties of Wide-Gap II–VI Low-Dimensional Semiconductors NATO ASI Series Volume 200, 1989, pp 75-85 and refs. therein
The Growth of Thin Layers by MOCVD of Wide Band Gap II-VI Compounds
http://link.springer.com/chapter/10.1007/978-1-4684-5661-5_8
http://link.springer.com/chapter/10.1007/978-1-4684-5661-5_8#page-1
[iii] T J Gregory, J E Nicholls, J J Davies, J O Williams and N Maung, Semicond. Sci. Technol. 1988, 3 1193 doi:10.1088/0268-1242/3/12/007, http://iopscience.iop.org/0268-1242/3/12/007 , “Magnetic-field-induced destabilisation of excitons bound at neutral donors in epitaxial Zn1-xMnxSe”
Mn(MeCp)(CO)3 for Cd1-xMnxTe films by MOCVD
Methylcyclopentadienyl manganese tricarbonyl Mn(MeCp)(CO)3) was applied as Mn source for the MOCVD growth of single crystal Cd1−x Mn x Te (x=0.10–0.30) films on (111) GaAs substrates, with and without CdTe buffer layers, at substrate temperatures 380°-450°C. The films grown at 420° C substrate temperature had reasonable Mn concentration (>10%) and had good quality, according to IR phonon spectra and Raman measurements. Mn concentration in agreement with PL measurements and layer thickness was determined from spectral analysis.[[i][PS1] ]
Tricarbonyl methylcyclopentadienyl manganese Mn(MeCp)(CO)3) was applied as Mn precursor for the MOCVD deposition of CdMnTe films (with a target bandgap of 1.8 eV for solar cell applications) on g1ass/SnO2/CdS substrates (with CdMe2 and TeEt2 as Cd, Te sources).
The bandgap, compositional uniformity, and interface quality of the films were determined by XRD, surface photovoltage spectroscopy, and AES measurements. Front-wall CdMnTe cell (glass/SnO2/CdS/CdMnTe/ZnTe/metal) efficiency was ~6%. The n-i-p cell efficiency was higher than those of the n-p cells. [[ii][PS2] ]
Tricarbonyl (methylcyclopentadienyl) manganese Mn(MeCp)(CO)3), in combination with CdMe2 and TeEt2, has been applied as Mn precursor for MOCVD growth of Cd1−xMnxTe films on (100)2°[011] GaAs substrates in a horizontal quartz reactor at atmospheric pressure with an RF- heated graphite susceptor. The grown films were characterised by electron diffraction and high resolution electron microscopy. Cd1−xMnxTe films films grown 420°C (x=0.3) and 450°C (x=0.5) were found to have dramatically different microstructures: two orientation relationships of the epilayers with respect to the substrate were observed, what could be related to GaAs substrate surface morphology.[[iii][PS3] ]
Tricarbonyl (methylcyclopentadienyl) manganese (TCPMn) Mn(MeCp)(CO)3 has been applied as Mn source (combined with CdMe2, TeEt2 as Cd, Te sources) for the heteroepitaxial growth of the dilute magnetic semiconductor alloy Cd1−xMn xTe on GaAs by MOCVD. Mn(MeCp)(CO)3 precursor had to be heated to as high as 140 °C to provide the required vapor pressure. Cd1−xMn xTe films with Mn atomic fractions up to 30% have been grown at 410–450 °C temperatures. Good quality and good surface morphology of the grown films was shown by optical absorption/transmission, PL, XRD and SEM measurements.[[iv][PS4] ]
Tricarbonyl(methylcyclopentadienyl) manganese (TCPMn) Mn(MeCp)(CO)3 was used as Mn source (in combnation with CdMe2 and TeEt2 as Cd and Te sources) for the heteroepitaxial growth of (CdMn)Te on (100) GaAs and glass substrates by atmospheric pressure MOCVD in a horizontal quartz reactor with an RF-heated graphite susceptor, with high purity H2 as carrier gas (total flow rate ca. 4 slm, corresponding to a linear flow velocity of about 3 cm/sec over the substrate). GaAs (100) substrates (2° (110) misoriented) were applied, they were cleaned in organic solvents and etched with a H2 SO4 :H2 O2 :H2 O solution (5:1:1) for 30 seconds. The partial pressures of the Cd (heated at 0°C) and Te sources (heated at 27°C) were typically ~8×10-5 atm and ~1.6×10-4 atm, respectively (deposition was carried out at atmospheric pressure). The TCPMn source was heated to a temperature in the range of 120° C. to 140° C, substrate temperatures were ~ 410° - 450° C.
A series of depositions were made on glass substrates, the energy bandgap / percentage of Mn was determined from optical transmission measurements. F.e., from optical transmission curves for a CdTe film and two Cd1-x Mnx Te films with x=0.2 and 0.3, the extrapolated bandgap energies (assuming constant reflection over the wavelength range) was ~1.52, 1.77 and 1.87 eV, respectively. These data matched quite well with similar data reported for Cd1-x Mnx Te films deposited by ionized cluster beams.
The orientation of the Cd1-x Mnx Te crystalline layer on (100) GaAs was either (100) or (111), depending on the initial growth conditions. Strong photoluminescence was observed at low temperatures (10-15K) in Cd1-x Mnx Te films grown on (100) GaAs excited by a 488 nm Ar laser. In the PL spectrum for a Cd0.75 Mn0.25 Te film at T=10K, the FWHM ~33 meV was an indication of the good crystalline quality of the layer.
For (CdMn)Te layers, morphology haziness was observed in some cases (whereas CdTe films were featureless mirror-like). By optimising carrier gas flow, Te to Cd/Mn mole fraction ratio, and substrate temperature, allowed to obtain (CdMn)Te films having a smooth and mirrorlike surface morphology. To avoid milkiness of the layers, the importance of remaining below 440° C when growing (Cd,Mn)Te on GaAs by MOCVD was determined, due to suspected formation of Te crystallites on the substrate in films grown above that temperature. A very light ripple effect with features having dimensions of only about several thousand angstroms at the surface of an exemplary (CdMn)Te was found by SEM.[[v][PS5] ]
[i] R. Sudharsanan, Z. C. Feng, S. Perkowitz, A. Rohatgi, K. T. Pollard, A. Erbil
J. Electron. Mater., 1989, Vol. 18, Iss. 3, p.453-455,
Characterization of MOCVD-grown CdMnTe films by infrared spectroscopy
[ii] Rohatgi, A., Sudharsanan, R. ; Ringel, S.A. ; Meyers, P.V. ; Liu, C.H., Photovoltaic Specialists Conference, 1988., Conference Record of the Twentieth IEEE, Date of Conference:1988, Page(s): 1477 - 1481 vol.2, DOI : 10.1109/PVSC.1988.105955
“ Wide bandgap thin film solar cells from CdTe alloys”
[iii] J. H. Mazur, P. Grodzinski, A. Nouhi, R. J. Stirn, MRS Proceedings, Vol. 102 ,1987, DOI: http://dx.doi.org/10.1557/PROC-102-337, “ High Resolution Transmission Electron Microscopy Investigation of the Defect Structure in CdMnTe Layers Grown on GaAs by MOCVD
http://journals.cambridge.org/action/displayAbstract?fromPage=online&aid=8176938
[iv]Akbar Nouhi, Richard J. Stirn, Appl. Phys. Lett. 51, 2251 (1987); DOI 10.1063/1.98927, http://scitation.aip.org/content/aip/journal/apl/51/26/10.1063/1.98927
„Heteroepitaxial growth of Cd1−x Mn x Te on GaAs by metalorganic chemical vapor deposition”
[v] Akbar Nouhi, Richard J. Stirn, US 4935383 A, 1990
http://www.google.com/patents/US4935383 “Preparation of dilute magnetic semiconductor films by metalorganic chemical vapor deposition”
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