HAL Id: hal-01560926
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Submitted on 19 Jul 2017
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P-type transition metal carbodiimides MNCN (M = Ni,
Mn)
Baptiste Polteau, Franck Tessier, François Cheviré, Adèle Renaud, Laurent
Cario, Tengfei Jiang, Stéphane Jobic
To cite this version:
Baptiste Polteau, Franck Tessier, François Cheviré, Adèle Renaud, Laurent Cario, et al.. P-type tran-sition metal carbodiimides MNCN (M = Ni, Mn). 6th International Symposium on Structure-Property Relationship in Solid State Materials (SPSSM-2016), Jul 2017, Nantes, France. �hal-01560926�
Eaptiste Polteaua2 Vranck Tessiera2 Vrançois 5heviréa2 4dèle Renauda
Laurent 5ariob2 Tengfei Jiangb2 Stéphane Jobicb
aInstitut des Sciences Chimiques de Rennes -UMR CNRS 6226yg Université de Rennes 1g France bInstitut des Matériaux Jean Rouxelg -UMR CNRS 6532yg Université de Nantesg France
Over the last decade2 p+type semiconductors wS5. have known a renewed interest3 Indeed these materials may have potential
applications for light+emitting diodes2 transistors2 solar cells2 etc3 Since the stabilization of the �irst p+type semi+conductor 5u4lO9with a
delafossite structure type w4zE7zO
9. by H3 Kawazoe in 1::… [1]2 many p+type semiconductors with the same structure have been
reported such as 5u?aO92 5u5rO92 5uScO9… Recently2 X3 Liu etÅ al have reported the synthesis and the structure determination of a new
family of materialsM the transition metal carbodiimides MN5N wwith M W Mn → 5u. [927]3 These materials adopt a structure type related
to the delafossite2 formed by a divalent transition metal and N5N9+ anion3 We report here the synthesis and the microstructural
characterization of two transition metal carbodiimides MnN5N and NiN5N3 Impedance measurements demonstrate the p+type conductivity of these materials3
References
p9type characterization
P+type transition metal carbodiimides
MN5N wM W Ni2 Mn.
Nickel carbodiimide -NiNCNy
Manganese carbodiimide -MnNCNy
Structure a c A F N N ] ] A= 1Å29 Å 2Å24 Å b A B B C C A A B B F N N ] ] A= 1Å34 Å 2Å36 Å a c b NibNOvFsW mHsO HsCNsyHsO Precipitation Route NH-OH bh* KwtF Green Precipitate
Dark blue solution NibNHvFmsS NHv Stirring Overnight Washing Drying Light blue precipitate NibHNCNFs End of Precipitation Precursor Nickel precursor synthesis
NibHNCNFs S LiClyKCl -my*- bKwtgF Tubular Furnace Time Tamb 1K°53min+1 8well 9 9[ h 955 °F NAfgk 8well 1 19 h ,,5 °F
NiN5N synthesis XR8 patterns
Structure S6M ]X: nm ]7: nm 9G nm 9: nm 1KK nm 1 μm MnCOvS HsCNs Tubular Furnace Time Tamb 1K°53min+1 8well 9 hours 955 °F NH,fgk NAfgk MnN5N synthesis S6M XR8 patterns 1 μm K27[ μm K27: μm 1KK nm 711 nm 9[9 nm 6lectrochemical assembly Counter Electrode bPtF Reference
Electrode bSCEF Working Electrode
Electrolyte bLiClO-F
SC
Measurements carried out on pressed pellets fSFk sintered at ,55 °F under NAin lithium perchlorate electrolyte Energy feVk 5E EF VE Eredox -+ + + + + -- -h6 e=- ---+++ + + + -+++ + + + -+++ + + + n+type S5 6lectrolyte E n9type semiconductor -+ Helmholtz -+- -Energy feVk 5E EF VE Eredox -+ + + + + + + -- -+ + -h6 e= -+- -+- -+ + + + + + + + + E p9type semiconductor p+type S5 6lectrolyte Helmholtz
NiN5N and MnN5N conductivities °
C-2 Potential (E) Efb C-2 Potential (E) Efb + + + + -C + + + + -C
Mott Schottky plot
Positive slope
nktype SC Negative slopepktype SC
Negative slopes L p=type conductivity of NiNFN and MnNFN M by Rietveld re�inement
Nickel hydrogencyanamide precursor
Space group Px,1mmc fa K ,.7*9% D�/ c K 8.Ax7 D�k Fhemical formula NiF7.7*NA.58P
Exp zwt. N K A8.7 z fTheo. K Aw.,% zk Speci�ic surface area ≈ %* mA.g=7 Platelets ∼ x55 nm x ,5 nm Light brown color
Manganese carbonate precursor Space group L R =, m fa K ,.,xw D�/ c K 79.,9 D�k
Fhemical formula L MnF5.89NA.A7P Exp zwt. N K ,,., z fTheo. K A8.*5 zk
Speci�ic surface area ≈ AA mA.g=7 Dgglomerated particles f∼ ,55 nmk Light grey color
M by Rietveld re�inement
[7] Kawazoe/ H.R Yasukawa/ M.R Hyodo/ H.R Kurita/ M.R Yanagi/ H.R Hosono/ H. Nature 1::…/ ,w8/ 8,8. [A] Liu/ X.R Krott/ M.R Muller/ P.R Hu/ F.R Lueken/ H.R Bronskowski/ R. Inorg. Fhem. 9KK]/ 99/ ,557. [,] Krott/ M.R Liu/ X.R Fokwa/ I. P.R Speldrich/ M.R Lueken/ H.R Bronskowski/ R. Inorg. Fhem. 9KK…/ 9x/ AA59.
5apacitance measurements
SCyElectrolyte interface
