Unconventional synthesis methods for solid state...

Unconventional synthesis methodsfor solid state materials

Julia V. Zaikina

Chemistry Department, Iowa State University

Material discovery starts with synthesis...

steel plastic glass cement

solar panels superconductors QLED TV thermoelectrics

Structure

Synthesis

Properties

Synthesis

Structure

Material

Processing

Material

Chemistry

Materials Science

Theory

Structure

Synthesis

Properties

Synthesis

Structure

Material

Processing

Material

Chemistry

Materials Science

Theory

M. Jansen. Angew. Chem. Int. Ed. 2002, 41, 3746 ‐ 3766.

Solid State Synthesis is challenging...

Patnaik, S; Sadow, A. D. Angew. Chem. Int. Ed. 2019Walker, J. A.; Vickerman, K. L.; Humke, J. N.; Stanley, L. M.

J. Am. Chem. Soc. 2017, 30, 10228–10231.

R. Zhang, J. P. Peterson, L. J. Fischer , A. Ellern, A. H. Winter J. Am. Chem. Soc. 2018, 140, 43, 14308‐14313

Robole, Z.; Rahn, K.; Lampkin, B. J.; Anand, R. K.; VanVeller, B.Journal of Organic Chemistry 2018

End of XX century: Exploratory Solid State Synthesis

F. J. DiSalvo. Science, 1990, 247, 649‐655

A. Cheetham. Science, 1994, 264, 794‐795

J. D. Corbett. Inorg. Chem. 2010, 49, 13‐28 F. J. DiSalvo. Pure Appl. Chem., 2000, 72, 1799‐1807

From Exploratory Solid State Synthesis to Synthesis by Design

M. Jansen. Angew. Chem. Int. Ed. 2002, 41, 3746 ‐ 3766.

“Even the longest voyage begins with the first step”Lao‐tse 64, about 400 B.C.

M. Jansen. Adv. Mater. 2015, 27, 3229–3242.

Challenges

or she

M. G. Kanatzidis. Inorg. Chem. 2017, 56, 3158−3173

Panoramic Synthesis or in‐situ reaction monitoring by high‐temperature powder X‐ray diffraction

D.P. Shoemaker, Y.‐J. Hu, D. Y. Chung, G. J. Halder, P.J. Chupas, L. Soderholm, J. F. Mitchell, M. G. Kanatzidis. PNAS, 2014, 111, 10922‐10927.

Cu + KSx ……..

V. Gvozdetskyi, B. Owens‐Baird, Sangki Hong, T. Cox, G. Bhaskar, J.V. Zaikina; manuscript in preparation. NaZn4Sb3

HT‐NaZn4Sb3

In‐situ reaction monitoring by high‐temperature powder X‐ray diffraction

An “easiest” task: a reproduction of published synthesis

Write your papers well

Read other’s papers well

Material Synthesis

Hans Georg von Schnering et al. Z. Anorg. Allgem. Chem. 2003, 629, 1256‐1264.

Material Synthesis

An “easiest” task: a reproduction of published synthesis

Write your papers well

Report all and every details including The sources of starting materials Heating and cooling ratesAny postsynthetic treatments

Material Synthesis

H2Ti3O7 in KOH media:

TiO2 + KOH H2Ti3O7 + ???

Multiple reports of hydrothermal synthesis of H2Ti3O7 in

KOH solution at pH = 14

Not reproducible, expected K2Ti3O7 forms instead.

Authors “forgot” to report about washing samples with

HCl after synthesis.

Indeed, K2Ti3O7 + HCl H2Ti3O7 + KCl

Material Synthesis

GeP synthesis

“All discussed phases were synthesized in the temperature

range 600‐1000C.” No other details!T. Wadsten. Acta Chem. Scand. 1967, 21, 593‐594

Several attempts to synthesize GeP failed until (after multiple

attempts) the T and cooling rate were figured out.

Material Synthesis

Lee, K.; Synnestvedt, S.; Bellard, M.; Kovnir. J. Solid State Chem. 2015, 224, 62‐70.

SiP2 synthesis

Do I need to go crazy and report moon phase and ampoule length?

For synthesis involving gas phase, i.e. all pnictides,

chalcogenides, halogenides ampoule volume matters.

SiP2 syntheses in standard 10cm long ampoules failed.

SiP2 syntheses in 18cm long ampoules were successful.

Material Synthesis

An “easiest” task: a reproduction of published synthesisRead other papers well!

Not only main text but also supporting information

Pay attention to description of synthesis of different compounds, not all samples might have been produced in a similar way

Devil is in the details: if details, like heating/cooling rates, are not given, try several different heating rates or contact an author of original publication

Request students’ thesis – often helpful despite some might be not written in English

Material Synthesis

Dolyniuk, J.; Owens‐Baird, B.; Wang, J.; Zaikina, J.V.; Kovnir, K. Clathrate Thermoelectrics. Materials Science & Engineering R. 2016, 108, 1‐46.

Slow Cool

• Seal under vacuum• Heat up• Cool down• Invert and Centrifuge• Harvest Crystals

Quartz Ampoule

Quartz Wool

Alumina Crucible

Layered Elements

Unconventinal Material SynthesisPart 1. Unconventional fluxes

M. G. Kanatzidis, R. Pöttgen, W. Jeitschko; Angew. Chem. Int. Ed. 2005, 44, 6996

P. Canfield. Solution Growth of Intermetallic Single Crystals: a Beginner’s Guide. In Properties and Application of Complex Intermetallics. 2010

30°C 938°CTmelting

Good flux Not so good flux

Other low‐meting metals: Sn, In, Pb, Hg, Al, Bi, etc….

Binary Alloy Phase Diagrams, 2nd Ed., Ed. T.B. Massalski, ASM International, Materials Park, Ohio, 1990, 3, 2406‐2408

La‐Ni eutectic

+ B + C La2BC

+ Mn + CLa11[MnC6]3

LaRu2Al2B

+ Mn + C + ELa21Mn8E7C12 E = Ge, Sn, Sb, Te, Bi

+ Ru + B + Al

Mn + Al + SnLa11M13Sn4‐ (M = Mn/Ni/Al)

Synthesis from La/Ni eutectic flux

J.V. Zaikina, et. al. Inorg. Chem. 2010, 49, 2773‐2781 J.V. Zaikina, et. al. J. Solid State Chem. 2010, 183, 2987

J.V. Zaikina, et. al. Chem. Mater. 2010, 22, 1846‐1853

Prof. Susan E. Latturner

J.V. Zaikina, et. al. Inorg. Chem., 2017, 56, 15194–15202.

Synthesis from La/Ni eutectic flux

La‐Ni eutectic

+ B + C La2BC

+ Mn + CLa11[MnC6]3

+ Mn + C + ELa21Mn8E7C12 E = Ge, Sn, Sb, Te, Bi

Sn(1)@La9

Sn(2)@La12

Spin‐frustration

Synthesis from eutectic halide fluxes

Powders of LiCl and CsCl, elemental Fe and Se were added together with the flux into an alumina crucible andsealed under partial Ar atmosphere.The ampoule was heated to a homogenization temperature of 715C, where it was kept for 1 h and then removedinto a preheated furnace at 457C. After slow cooling to 300C, it was quenched in water.

R. Hu, H. Lei, M. Abeykoon, E. S. Bozin, S. J. L. Billinge, J. B. Warren, T. Siegrist, C. Petrovic. Phys. Rev. B 2011, 83, 224502

Synthesis from polysulphide fluxes

Cu + KSx ……..

Standard ampoule synthesis: “shake and bake”

Temperature: check binary phase diagrams

Starting materials: Ru and Ge

Try to make RuGe, Tm > 1700 KRu + Ge good luck!

(Tm = 2607 K) (Tm = 1211 K)

Unconventinal Material SynthesisPart 2. Unconventional starting material

Binary Alloy Phase Diagrams, 2nd Ed., Ed. T.B. Massalski, ASM International, Materials Park, Ohio, 1990, 3, 2406‐2408

Starting materials: not necessary elements

Try to make RuGe, Tm > 1700 KRu + Ge good luck

(Tm = 2607 K) (Tm = 1211 K)

What about…3Ru + 3GeCl2 3RuGe + 2RuCl3 ?

Starting materials: not necessary elements

Try to make RuGe, Tm > 1700 KRu + Ge good luck

(Tm = 2607 K) (Tm = 1211 K)

What about…3Ru + 3GeCl2 3RuGe + 2RuCl3 ?

Y. Liu, L.‐M. Wu, L.‐H. Li, S.‐W. Du, J. D. Corbett, L. Chen. Angew. Chem. Int. Ed. 2009, 48, 5305 – 5308

Cs + Cd + Sb Cs8Cd18Sb28

Lu + Cd + Sb + CsClexcess Cs8Cd18Sb28 + LuCl3

A. Kaltzoglou, S. Ponou, T. F. Fässler. Eur. J. Inorg. Chem. 2008, 538–542.

K + Hg + Sn K8Hg4Sn42

K + Hg + Ge

K4Ge9 + Hg K8Hg4Ge42 (powders)

K4Ge9 + HgO + WO3 K8Hg4Ge42 (crystals)

A. Kaltzoglou, S. Ponou, T. F. Fässler. Eur. J. Inorg. Chem. 2008, 4507‐4510.

NaH + Si Na4Si4 + H2KH + Ge K4Ge4 + H2Kauzlarich, S.M. and co‐workers, Dalton Trans., 2009, 10250

better mixing easy to work with lower synthesis temperaturefaster than traditional solid‐state methodsreducing atmosphere prevents formation of oxide layers

J. V. Zaikina, M. Batuk, A. M. Abakumov, A. Navrotsky, S.M. Kauzlarich J. Am. Chem. Soc. 2014, 136, 16932

Hydride approach

Starting Materials Ball‐milled; for 30 min

Nb tube sealed with arc‐welder

KH + BaH2 + Fe + As Ba1‐xKxFe2As2 + H2

Hydride approach

Consolidate powder into dense pellet (>97%)

Applies pressure

Passes current through die & sample to raise temperaturePressure

Current

Spark‐Plasma Sintering (SPS)

Spark‐Plasma Sintering unit(upto 2200C and 20 kN)

In‐situ preparation and consolidation of BaFe2‐xCoxAs2via Spark‐Plasma Sintering (SPS)

J. V. Zaikina, M. Y. Kwong, B. Baccam, S.M. Kauzlarich. Chem. Mater. 2018, 30, 8883‐8890.

NaH + Si Na4Si4 + H2KH + Ge K4Ge4 + H2Kauzlarich, S.M. and co‐workers, Dalton Trans., 2009, 10250

better mixing easy to work with lower synthesis temperaturefaster than traditional solid‐state methodsreducing atmosphere prevents formation of oxide layers

Hydride approach toward synthesis of intermetallics

J. V. Zaikina, M. Y. Kwong, B. Baccam, S.M. Kauzlarich. Chem. Mater. 2018, accepted.

Hydride approach toward synthesis of intermetallics

T. Cox, V. Gvozdetskyi, B. Owens‐Baird, J. V. Zaikina. Chem. Mater., 2018, 30, 8707–8715.

V. Gvozdetskyi, M.P. Hanrahan, R.A. Ribeiro, T.H. Kim, L. Zhou, A.J.

Rossini, P.C. Canfield, J.V. Zaikina. Chem. Eur. J. 2019 Just Accepted.

LiH + Ni + B LiNi3B1.8 + H2

KH + Zn + Sb K8+xZn18+3xSb16 + H2

high‐temperature furnaces (up to 1200C) flow‐furnace

Unconventinal Material SynthesisPart 3. Unconventional heating

Spark‐Plasma Sintering unit(up to 2200C and 20 kN)

cold‐pressed bar shaped pellets

Ti + Ni + Sb TiNiSb

Ti + Co + Sb TiCoSb

evacuated quartz tubes

granular carbon as themicrowave susceptor inalumina insulation foam

Reactions were run at 100%power (700 W) for 1 min.After a ~ 2 sec. a purplish plasmawas observed through the gaps inthe housing surrounding thequartz tube which was followedby bright orange glow when thereaction was completed.

commercial microwave reactor(LG Goldstar)

No comparable reactiontakes place if no susceptormaterial is used

C.S. Birkel, W.G. Zeier, J.E. Douglas, B.R. Lettiere, C.E. Mills, G. Seward, A. Birkel, M.L. Snedaker, Y. Zhang, G. J. Snyder, T.M. Pollock, R. Seshadri, G.D. Stucky. Chem. Mater. 2012, 24, 2558–2565

cold‐pressed bar shaped pellets

Ti + Ni + Sb TiNiSb

Ti + Co + Sb TiCoSb

commercial microwave reactor(LG Goldstar)

• Energy‐saving preparative route• Faster (1 min vs. weeks)• No need for special setup

C.S. Birkel, W.G. Zeier, J.E. Douglas, B.R. Lettiere, C.E. Mills, G. Seward, A. Birkel, M.L. Snedaker, Y. Zhang, G. J. Snyder, T.M. Pollock, R. Seshadri, G.D. Stucky. Chem. Mater. 2012, 24, 2558–2565

Unconventional synthesis methods for solid state...

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