11/4/2015 Understanding and Designing Precursors for Chemical Vapor Deposition :: ChemViews Magazine :: ChemistryViews

Understanding and Designing Precursors for

Chemical Vapor Deposition
DOI: 10.1002/chemv.201500093
Author: Catharina Goedecke, Ralf Tonner
Published Date: 03 November 2015
Copyright: Wiley­VCH Verlag GmbH & Co. KGaA, Weinheim

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Dr. Ralf Tonner leads a junior research group for theoretical surface chemistry at the University of Marburg,
Germany. He talks to Catharina Goedecke for ChemViews Magazine about his recent research on precursors for
the functionalization of semiconductors and how he works at the interface between chemistry, physics, and
materials science.

The group looked at the decomposition of group 13 and group 15 compounds, such as gallanes or phosphines,
during their deposition on semiconductor surfaces. The resulting insights into the reaction mechanisms allow the
rational design of new precursors with desirable properties.

Would you please introduce your research?

I am a computational chemist, which means I use quantum mechanical methods to solve chemical problems. We
are working on surface chemistry, and our main interests in this rather broad research area are chemical bonding on
surfaces, at interfaces, and in materials, as well as interesting reactivity in these systems. This is rather unusual,
because in the field of extended systems, i.e, surfaces and solids, there are mainly people with a physics
background. They have a very different approach compared with chemists, who often take more of a local view on
these systems.

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Could you give an example of the chemistry problems you tackle

using these methods?
One main part of our research concerns the functionalization of semiconductors. We look at how we can change
semiconductor surfaces to give them new features for novel applications. We are doing this work at the interface
between chemistry, physics, and materials science. We are concerned with the elementary steps and the
chemistry in processes which deposit inorganic molecules on semiconductor surfaces. Our colleagues in physics
and in materials science can then build on these results.

What kinds of applications do these functionalized semiconductor

materials have?
Our materials science colleagues are, for example, working on improved solar cells with higher efficiency and on
optoelectronic devices based on silicon. Usually, silicon uses electrons for transferring information, but an
optoelectronic device uses light instead. This is interesting because light is much faster than electrons and also
produces less heat.

How are the semiconductor surfaces modified?

They are covered with a thin film of so­called III/V materials. These are composed of group 13 and group 15
elements, an example is gallium phosphide. The materials are grown on top of a silicon wafer using metal­organic
vapor phase epitaxy (MOVPE). This is a growth procedure where precursor molecules, usually in liquid form, are
evaporated and brought to the heated silicon surface. The molecules then decompose and form the desired film.
Common precursors are triethylgallane and tert­butylphosphine. We investigated the decomposition reactions of
these molecules [1].

Until few years ago, people used the hydrides, gallane or phosphane, to do this deposition, but they are toxic and
hard to handle. Additionally, the hydrides decompose only at very high temperatures, and our colleagues want to
grow metastable III/V materials, which require low growth temperatures. "Traditional" MOVPE is done at roughly
1000 °C, but if you want to grow these optically active materials, the temperature should be between 400 °C and
675 °C. This is where we come into play, because we can look at the decomposition channels of the precursors in
the gas phase and can get an idea of which reaction pathways are important and at which temperatures these
molecules decompose.

The network of pathways for a given reaction can be very complex.

How do you as computational chemist make sense of these many
possibilities and find the most likely path(s)?
You really have to think about which kind of reactions are possible. You can narrow the pathways down by
considering the experimental conditions. We know, for example, that the precursor is present only in a very low
concentration. That means that it’s very unlikely that two of the precursor molecules meet, so we only consider
unimolecular reactions. As a second experimental condition, we know that hydrogen is a carrier gas in the
experiment, so we also consider reactions with H2.

As a next step, we can, of course, look at the literature and get an idea of the possible pathways. This is where the
chemist’s experience really helps and where we can make valuable contributions. For chemists, it is often much

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easier to think in terms of reactivity and decomposition than for people with a physics background.

We know from the literature which classes of decomposition reactions can play a role, for example, homolytic
dissociation of bonds to form radicals. Heterolytic dissociation does not usually happen in the gas phase, because
generating ions is unfavorable. Lastly, certain elimination reactions can occur, as well. Once you picked the likely
reactions, you actually have to go and calculate the thermodynamics for the whole reaction network.

So you look at reaction energies and activation energies to figure out

what is feasible at the reaction temperature?
Yes. We apply a two­step procedure here, which we have used quite successfully for a number of precursors. First,
we look at the full reaction network by the thermodynamic approach. That is rather straightforward, because we
only look at ground state properties. We just compute the thermodynamics, and then we select the reactions which
are exergonic at the experimental conditions. If we have a reaction which has an enthalpy of, say, +200 kJ/mol, it is
unlikely to ever happen, so we don’t need to search for a transition state. We then search for transition states and
calculate activation energies only for the exothermic reactions, which are surprisingly few. This provides us with an
efficient approach to explore the likely reactions.

Which mechanisms are important for the decomposition reactions?

We found that homolytic bond cleavages, i.e., cutting a bond and forming radicals, are unfavorable. This was a bit
unexpected because in the literature there were many propositions and indirect evidence that these homolytic
dissociations may play a major role. Secondly, we found that especially β­hydrogen elimination reactions are very
important because they proved to have the lowest barrier for different precursors.

How do β­hydrogen eliminations work at an element such as

phosphorus?
That is what we wondered, as well, when we found this reaction pathway. For group 13 elements, β­hydride
elimination is textbook knowledge: You have an empty orbital into which a C­H bond can donate electron density in
a synchronous reaction. For gallium, for example, the gallium­hydrogen bond forms simultaneously with the
breaking of the gallium­carbon bond.

For the group 15 elements, β­hydrogen elimination was the dominant reaction channel, as well, even though there is
no empty acceptor orbital. We tried to understand that and performed an analysis of this reaction for the phosphorus
precursor, which we later extended to other group 15 elements [2]. Since there is no acceptor orbital, the
phosphorus­carbon bond has to break first and then the phosphorus­hydrogen bond can be formed in a later part of
the reaction.

What is the impact of these results?

We can use the results of our chemical bonding analysis and make predictions that are useful for finding good
precursors. For example, our calculations showed that the phosphorus­carbon bond breaking is the rate­determining
step. Thus, the carbon atom needs to be able to stabilize the positive charge occurring in the transition state.

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We looked for a way to stabilize this positive charge at this carbon atom better than with the tert­butyl substituent
which is used experimentally. We used the insight from the chemical bonding analysis and the calculated reaction
mechanism and tested different alkyl substituents. We increased the inductive effect to improve the ability of the
carbon atom to stabilize the positive charge.

We looked for a relationship between the stability of the carbocation and the transition barrier, and found that there
is a linear correlation [3]. This means the decomposition barrier can be predicted simply by the charge at this one
atom. After this, we thought: Why only use inductive effects? Why not also use orbital effects to stabilize this
carbocation? In organic chemistry, the β­silyl effect is well known and so we did what a computational chemist can
do: We simply substituted a hydrogen atom by a silyl group. We could show that the β­silyl effect actually
stabilizes the carbocation very strongly and lowers the decomposition barrier, so the result was a computational
chemistry­inspired precursor design.

How long did the investigation take?

It took essentially two thirds of a Ph.D. thesis, so between two and three years of research. The work has been
done by my student Andreas Stegmüller, who is first author on all three publications on the topic. This was the first
time that we investigated this type of chemistry, so we had to establish the methodology and find all the important
reactions. After Andreas’ initial work, we had several further publications and now even undergraduate students can
do follow­up work based on the project.

How did you follow up on these results?

We continued to work on the topic of III­V materials on silicon. We were also approached by the Swedish group of
Henrik Pedersen, an experimentalist, and just had a joint paper on how to deposit boron carbide films on surfaces
published [4]. Additionally, we are collaborating more closely on new precursors with our colleagues in inorganic
chemistry and materials science at the University of Marburg. Together, we proposed a new single­source precursor
for arsenic and nitrogen, also based on this type of decomposition chemistry. We have also organized a workshop
on the topic of chemistry­driven growth processes, which will bring together experts on the topic from different
communities in November 2015.

Thank you very much for the interview.

References

[1] A quantum chemical study on gas phase decomposition pathways of triethylgallane (TEG, Ga(C2H5)3) and tert­
butylphosphine (TBP, PH2(t­C4H9)) under MOVPE conditions,
Andreas Stegmüller, Phil Rosenow, Ralf Tonner,
Phys. Chem. Chem. Phys. 2014, 16, 17018–17029.
DOI: 10.1039/c4cp01584c
[2] β­Hydrogen Elimination Mechanism in the Absence of Low­Lying Acceptor Orbitals in EH2(t­C4H9) (E = N–Bi),
Andreas Stegmüller, Ralf Tonner,
Inorg. Chem. 2015, 54, 6363–6372.
DOI: 10.1021/acs.inorgchem.5b00687
[3] A Quantum Chemical Descriptor for CVD Precursor Design: Predicting Decomposition Rates of TBP and TBAs
Isomers and Derivatives,
Andreas Stegmüller, Ralf Tonner,
Chem. Vap. Deposition 2015, 21, 161–165.
DOI: 10.1002/cvde.201504332

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[4] Gas phase chemical vapor deposition chemistry of triethylboron probed by boron–carbon thin film deposition and
quantum chemical calculations,
Mewlude Imam, Konstantin Gaul, Andreas Stegmüller, Carina Höglund, Jens Jensen, Lars Hultman, Jens Birch,
Ralf Tonner, Henrik Pedersen,
J. Mater. Chem. C 2015.
DOI: 10.1039/c5tc02293b

Ralf Tonner studied chemistry at the Universities of Marburg, Germany, and Auckland,
New Zealand. He received his Ph.D. in theoretical chemistry from the University of
Marburg in 2007 under the supervision of Gernot Frenking. After a postdoctoral stay with
Peter Schwerdtfeger at Massey University, Auckland, New Zealand, Dr. Tonner returned to
Marburg in 2010 as Group Leader in theoretical chemistry.

His research interests include the ab initio description of chemical bonding and reactivity at
surfaces, using mainly density functional but also wavefunction based methods in
periodical and non­periodical approaches.

Selected Publications

A periodic energy decomposition analysis method for the investigation of chemical bonding in extended systems,
Marc Raupach, Ralf Tonner,
J. Chem. Phys. 2015, 142, 194105.
DOI: 10.1063/1.4919943
Rhodium(I) and Iridium(I) Complexes of the Conformationally Rigid IBioxMe4 Ligand: Computational and
Experimental Studies of Unusually Tilted NHC Coordination Geometries,
Jan­Niclas Luy, Simone A. Hauser, Adrian B. Chaplin, Ralf Tonner,
Organometallics 2015, 34, 5099–5112.
DOI: 10.1021/acs.organomet.5b00692
Complex Surface Chemistry of an Otherwise Inert Solvent Molecule: Tetrahydrofuran on Si(001),
Gerson Mette, Marcel Reutzel, Ruben Bartholomäus, Slimane Laref, Ralf Tonner, Michael Dürr, Ulrich Koert, Ulrich
Höfer,
ChemPhysChem 2014, 15, 3725–3728.
DOI: 10.1002/cphc.201402486
Adsorption of Proline and Glycine on the TiO2 (110) Surface: A Density Functional Theory Study,
Ralf Tonner,
ChemPhysChem 2010, 11, 1053–1061.
DOI: 10.1002/cphc.200900902
Bonding Analysis of N­Heterocyclic Carbene Tautomers and Phosphine Ligands in Transition­Metal Complexes: A
Theoretical Study,
Ralf Tonner, Greta Heydenrych, Gernot Frenking,
Chem. Asian J. 2007, 2, 1555–1567.
DOI: 10.1002/asia.200700235
C(NHC)2: Divalent Carbon(0) Compounds with N­Heterocyclic Carbene Ligands – Theoretical Evidence for a Class
of Molecules with Promising Chemical Properties,
Ralf Tonner, Gernot Frenking,
Angew. Chem. Int. Ed. 2007, 46, 8695–8698.
DOI: 10.1002/anie.200701632
Carbodiphosphoranes: The Chemistry of Divalent Carbon(0),
Ralf Tonner, Florian Öxler, Bernhard Neumüller, Wolfgang Petz, Gernot Frenking,
Angew. Chem. Int. Ed. 2006, 45, 8038–8042.
DOI: 10.1002/anie.200602552

Also of Interest

How Many Atoms Fit Into C60?,

ChemViews Mag. 2011.
How many rare gas atoms can be placed into a fullerene cage until the pressure becomes large enough to break the
framework?

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Tonner Group, Marburg, Germany

Event: CECAM/Psi­k/HERALD Workshop,
Simulation of chemistry­driven growth phenomena for metastable materials

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