Coordination Chemistry Reviews 257 (2013) 3297–3322

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Coordination Chemistry Reviews

journal homepage: www.elsevier.com/locate/ccr

Review

Precursors as enablers of ALD technology: Contributions from

University of Helsinki
Timo Hatanpää ∗ , Mikko Ritala, Markku Leskelä
Laboratory of Inorganic Chemistry, Department of Chemistry, University of Helsinki, P.O.Box 55, 00014 University of Helsinki, Finland

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3298
2. Alkaline earth metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3298
2.1. ␤-Diketonates of alkaline earth metals as precursors for ALD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3299
2.2. Cyclopentadienyl compounds of alkaline earth metals as precursors for ALD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3300
3. Group 4 elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3305
3.1. Group 4 metal halides as precursors for ALD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3305
3.2. Group 4 alkoxides as precursors for ALD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3306
3.3. Group 4 alkylamides as precursors for ALD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3307
3.4. Group 4 Cyclopentadienyl compounds for ALD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3307
3.4.1. Bis-cyclopentadienyl compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3307
3.4.2. Mono-cyclopentadienyl compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3307
3.5. Other group 4 precursors for ALD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3308
4. Group 15 and 16 elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3309
4.1. Alkylsilyl compounds of group 15 and 16 elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3309
5. Bismuth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3311
5.1. Bismuth chloride as precursor for ALD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3312
5.2. Organometallic compounds of bismuth as precursors for ALD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3312
5.3. Tris(Bis(Trimethylsilyl)amido)Bismuth(III) as a precursor for ALD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3312
5.4. Bismuth compounds with oxygen based ligands as precursors for ALD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3313
5.4.1. ␤-Diketonates of bismuth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3313
5.4.2. Bismuth alkoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3313
5.4.3. Bismuth carboxylates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3315
6. Pt group metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3315
7. Silver . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3315
8. Summary and conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3319
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3319

Abbreviations: acac, acetylacetonate; ALD, atomic layer deposition; CET, capacitance equivalent thickness; CHT, cycloheptatrienyl; CHD, cyclohexadiene; CMOS, comple-
mentary metal oxide semiconductor; CN, coordination number; Cp, cyclopentadienide; COD, cyclooctadiene; CVD, chemical vapour deposition; dien, diethylenetriamine;
diglyme, bis(2-methoxyethyl) ether; DMAE, dimethylaminoethoxide; DRAM, Dynamic random access memory; EDS, energy dispersive spectrometry; EOT, Equivalent oxide
thickness; FESEM, field emission scanning electron microscope; fod, 1,1,1,2,2,3,3-heptafluro-7,7-dimethyl-4,6-octanedione; FRAM, ferroelectric random access memory;
GST, Germanium antimony telluride; hfac, hexafluoroacetylacetonate; HRTEM, high resolution transmission electron microscopy; me, methoxyethoxy; mmp, 1-methoxy-
2-methyl-2-propanolate; MOCVD, metal organic chemical vapour deposition; MS, mass spectroscopy; MTHD, methoxy-2,2,6,6-tetramethylheptane-3,5-heptanedione, me;
METHD, methoxyethoxy-2,2,6,6-tetramethylheptane-3,5-heptanedione; MOSFET, metal oxide semiconductor field effect transistor; NVRAM, non-volatile random access
memory; PCRAM, Phase change random access memory; PEALD, plasma enhanced atomic layer deposition; Piv, pivalate; REALD, radical enhanced atomic layer depo-
sition; SBT, strontium bismuth tantalate; SDTA, single differential thermal analysis; SEM, scanning electron microscope; SIMS, Secondary ion mass spectrometry; SOFC,
solid oxide fuel cell; TG, thermo gravimetry; TGA, thermo gravimetric analysis; THF, tetrahydrofurane; tmhd, tetramethylheptanedione; Tp, tris(pyrazolyl)borate; TpEt2 ,
tris(3,5-diethylpyrazolyl)borate; trien, triethylenetetraamine; triglyme, triethylene glycol dimethyl ether.
∗ Corresponding author. Tel.: +358 919150222, fax: +358 919150198.
E-mail address: timo.hatanpaa@helsinki.fi (T. Hatanpää).

0010-8545/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.ccr.2013.07.002
3298 T. Hatanpää et al. / Coordination Chemistry Reviews 257 (2013) 3297–3322

a r t i c l e i n f o a b s t r a c t

Article history: The review focuses on ALD precursors of selected elements such as alkaline earth (Mg, Ca, Sr, Ba), group
Received 4 March 2013 4 metals, bismuth, silver, iridium, selenium, tellurium and antimony. These elements are needed in dif-
Received in revised form 3 July 2013 ferent high tech applications but are challenging for ALD. Their precursor design needs careful balancing
Accepted 3 July 2013
between volatility, thermal stability and reactivity—the key properties of ALD precursors. The extensive
Available online 18 July 2013
studies showed that cyclopentadienyl based precursors of alkaline earth metals are versatile ALD pre-
cursors which react with both water and ozone forming oxide. Group 4 ALD chemistry has been studied
Keywords:
very widely and many good precursors have been found for the oxide ALD. From a bunch of different
Atomic layer deposition
ALD precursors
compound types studied the most promising ALD precursor for bismuth is Bi(OCMe2 i Pr)3 which shows
High-K materials stable ALD process with water at 150–250 ◦ C. The success in depositing noble metal films by ALD can
Phase change memory be attributed more to the reactant rather than the metal precursor. Ru, Pt, Ir, Rh and Os films can be
Alkaline earth metals deposited from various organometallic and metal organic precursors using O2 as the other precursor.
Group 4 metals Typically temperatures above 225 ◦ C are needed. Using O3 as a reactant films can be deposited at lower
Bismuth temperatures. Noble metal oxides are obtained below approx. 200 ◦ C and metallic films above that. By
Iridium supplying both O3 and H2 as consecutive pulses, noble metal films can be deposited well below 200 ◦ C.
Silver
For silver phosphine stabilized carboxylato and ␤-diketonato complexes are thermally stable enough
enabling hydrogen plasma enhanced ALD of silver metal films. Alkylsilyl compounds of selenium and
tellurium are versatile ALD precursors for metal selenide and telluride films when combined with metal
chloride precursors. The use of alkylsilyl compounds is not limited to group 16 elements but can also
been used for group 15.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction
The success of ALD is built on chemistry. The great benefits of
ALD (conformality, uniformity, atomic level thickness control, etc.)
can be enjoyed only when proper precursors have been identified
for the material of an interest. The precursors need to meet a num-
ber of requirements (Table 1) among which the combination of
high reactivity and good thermal stability often sets major chal-
lenges. Volatility is important too, and though moderately volatile
solids are used even industrially, liquids and gases are preferred for
convenience.
The ALD chemistry has been approached from two directions:
scientific curiosity and from needs of industry. Over the years the
emphasis has been shifted toward the latter as the ALD has become
better known and more widely used thin film deposition technique.
For example, when we in 1993 studied HfCl4 as a precursor for
ALD of HfO2 [1] this was done for comparison to the earlier stud-
ied TiCl4 [2], and neither we nor anyone else had a clue that ALD
HfO2 would become a high-k gate oxide in the leading MOSFETs
15 years later. By contrast, our recent breakthrough in ALD of tel-
lurides and selenides with their alkylsilyl compounds as precursors
[3], was motivated by a request addressed to us from semiconduc-
tor companies via an ALD tool manufacturer that we collaborate
with. On the other hand, also in 1990s we did application motivated
precursor research but that focused on electroluminescent dis-
play materials rather than the current mainstream semiconductors.
Soon after the results and knowledge gained in that research were
successfully benefited in developing an ALD process for SrTiO3 [4]
that had gained increasing interest in IC applications because of its
very high-k value.
ALD metal precursors have traditionally been grouped based
on their ligands (Fig. 1): halides, ␤-diketonates, alkoxides, alkyl
amides, alkyls, cyclopentadienyls, amidinates, guanidinates, etc.
and even elements [5]. Inside these groups the precursor properties
have been tuned to meet the ALD requirements by tailoring the lig-
ands, particularly by changing the size of the ligands and by adding
donor functionalities to the hydrocarbon groups of the ligands.
Another option has been to add adduct ligand to the coordination
sphere of the metals. A newer trend has involved heteroleptic metal
complexes where two or more different ligands are used together
for further tuning of the precursor properties.
In this paper we review some of our own contributions to the
ALD precursor chemistry over the past 20 years. The aim of the
review is not to present a balanced view of the field but to focus
on studies and discoveries done at the University of Helsinki. Thus
references to other studies are kept in minimum. A number of
different kinds of precursor groups will be covered. Each chapter
begins with a brief summary of applications of ALD films containing
the given elements, thereby demonstrating how in ALD precur-
sor chemistry basic and applied research are connected seamlessly.
Properties (structure, volatility, thermal stability, reactivity) of pre-
cursors studied and main results from the film growth experiments
are reviewed. About the ALD reaction mechanisms only some illus-
trative examples will be given since in situ reaction mechanism
studies on ALD processes were reviewed in detail very recently by
Knapas and Ritala [6].
2. Alkaline earth metals
Alkaline-earth metals are constituents of many technologically
important materials. SrTiO3 and Ba1−x Srx TiO3 are high permit-
tivity dielectric materials for future DRAMs [7]. BaTiO3 is not
only a dielectric but also piezoelectric and ferroelectric material
which may be used in e.g. ceramic multilayer capacitors and ther-
mistor elements [8,9]. CaS, SrS and BaS are host materials for
luminescent materials [10,11]. SrBi2 Ta2 O9 is a ferroelectric mate-
rial which may be used in FRAMs [12]. Strontium and barium
are also constituents of the well-known superconducting cuprates
La2−x Srx CuO2 , YBa2 Cu3 O7−x and Bi2 Sr2 CaCu2 O8+x [13]. Fluorides of
magnesium and calcium are materials suited for optical coatings
[14].
Especially the larger alkaline earth metals are challenging from
the CVD/ALD precursor chemistry point of view: their compounds
have a tendency to form oligomeric species which have low
volatility. Thus sufficiently volatile, thermally stable and reactive
compounds of alkaline earth metals are not that common.
Before the interest in ALD, a large variety of ␤-diketonates and
also many other compounds had been used in CVD as precur-
sors for alkaline earth metals. In addition a variety of compounds
had been suggested as possible precursors due to their volatil-
ity [15]. These compounds include silylamides and phosphides,
poly(pyrazaolyl)borates, alkoxides, ␤-ketoiminates, pyrazolates,
pyrrolates and cyclopentadienyl compounds with and without
neutral ancillary Lewis base ligands. Precursors used for ALD of
alkaline-earth metal containing films are quite few and they are col-
lected into Table 2. Basically the precursors have been restricted to
 T. Hatanpää et al. / Coordination Chemistry Reviews 257 (2013) 3297–3322 3299

Fig. 1. General classes of metal precursors. Backbones of the ligands are shown and in addition the ligands may contain donorfuntionalities in the variable Rx parts.

␤-diketonates and cyclopentadienyl compounds which have been
extensively studied at the University of Helsinki too.
2.1. ˇ-Diketonates of alkaline earth metals as precursors for ALD
four metal centers have been reported for “Ba(thd)2 ” [118] and
if additional aqua, OH or O ligands are coordinated the size of
oligomers increases further [119]. By using neutral adduct ligands
such as polyethers and polyamines it is possible to decrease the

Table 1
The first alkaline-earth metal compounds introduced as precur-
Requirements for ALD precursors.
sors for ALD were ␤-diketonates. These are the most well-known
volatile compounds of alkaline earth metals. Their volatilization Requirement Comment
properties have been known for decades [116] but the real boom Volatility Volatility is needed for efficient
came in connection to high-temperature superconductors. The transportation. For stable flux liquids
CVD of oxide superconductors required volatile compounds for and gases are preferable.
Thermal stability Decomposition of precursors is not
Ca, Sr and Ba as well as for rare earths [117]. The number of dif-
allowed. Instability would destroy the
ferent ␤-diketonato ligands is high but by far the most used is self-limiting film growth mechanism
the thd-ligand (thd = 2,2,6,6-tetramethyl-3,5-heptanedione). The of ALD.
␤-diketonates have several advantages such as sufficiently easy Reactivity Aggressive and complete reactions
synthesis and reasonable thermal stability but also several disad- with co-precursors to ensure fast
completion of surface reactions and
vantages like limited volatility because of oligomerization and low thus short cycle times, and for high
reactivity. In thin film growth experiments there have also been film purity.
problems which have been associated with some kind of instability No etching of the film or Competing reactions may prevent film
of the ␤-diketonate precursors at their evaporation temperatures substrate material growth.
Unreactive and volatile To avoid corrosion. Readsorption of the
[44]. This behavior may have been partly related to the quality of
byproducts byproducts may slow the film growth.
the thd-compounds as the actual precursors used may have been No dissolution into the film or Would destroy the self-limiting growth
different O and OH groups containing oligomeric species formed substrate behavior.
when different synthesis methods without exclusion of water and Purity Sufficiently pure precursors to meet
air have been used, or the compounds have been handled or stored the requirements specific to each
application.
incorrectly. Inexpensive Easy synthesis with good yield, simple
The large size and low charge of alkaline earth metal ions compounds with cheap ligands.
and only bidentate character of the ␤-diketonato ligands causes Easy to handle Stable at ambient air, if possible.
coordinative unsaturation in M(␤-diketonato)2 complexes. The Non-toxic and If possible.
environmentally friendly
unsaturation is decreased by oligomerization and oligomers with
3300 T. Hatanpää et al. / Coordination Chemistry Reviews 257 (2013) 3297–3322
molecule size to monomolecular one [120]. The volatility of the
alkaline earth thd complexes increases in series Ba < Sr < Ca < Mg
and this is in line with the oligomerization and ion size. “Sr(thd)2 ”
and “Ca(thd)2 ” form trimers when crystallized in dry organic
solvents and also need an adduct ligand such as polyamines
or polyethers to be monomolecular [41,121]. The mass spectro-
metric studies show that also in gas phase the alkaline earth
thd-complexes exist in oligomeric forms with the dimeric species
being the dominant in the mass spectra [116,122]. Magnesium as
the smallest member in the series forms a dimeric thd-complex
[21] which again can be turned to monomeric by ancillary neu-
tral ligands [123]. The mass spectrometric and sublimation studies
of adducted thd-complexes of the larger alkaline earth metals Sr
and Ba suggest that the neutral ligand dissociates upon sublima-
tion or in the gas phase—in this sense adducts with fluorinated
␤-diketonato ligands are better because many of them evaporate as
intact molecules. The thd-complexes of Mg and Ca make an excep-
tion: diamine and polyamine adducts stay intact in the gas phase
below a certain dissociation temperature [41,123].
Alkaline earth metal thd-complexes have been used in ALD to
deposit the corresponding sulfides and fluorides using H2 S and HF
as the co-precursors, respectively [10,35,37–41,44–47,110]. CaS,
SrS and BaS films doped with different rare earth metal ions
have extensively been studied as phosphor materials for electro-
luminescent flat panel displays [10,11]. Fluorides have also been
deposited using reactions between the thd-complexes and TiF4 and
TaF5 .[18–20,36] This method avoids the usage of highly corrosive
and toxic HF and also much higher growth rates were obtained,
e.g. with the Ca(thd)2 + TiF4 process a four times higher growth rate
(1.6 Å/cycle) compared to the Ca(thd)2 + HF process was achieved.
In contrast to H2 S and HF, water does not react effectively
with the ␤-diketonates of larger alkaline earth metals at tem-
peratures below decomposition [44]. This insufficient reactivity
of ␤-diketonates is the main limitation for their usage in ALD of
oxide films. However, growth of an oxide by the Cathd2 + H2 O pro-
cess has been reported [32] and in two studies SrO also grew,
though with a low rate of 0.1 Å/cycle, from Sr(thd)2 and H2 O
at 250 ◦ C [50,55]. Also when Sr(thd)2 + H2 O cycles were mixed
with Ti(Oi Pr)4 + H2 O or Ti(Oi Pr)2 (thd)2 cycles SrTiO3 films could be
grown [50,55].
Because water has low reactivity with ␤-diketonates more reac-
tive oxygen sources have been introduced. Ozone is the common
second choice for oxygen precursor in ALD of oxide films. With thd-
complexes of the larger alkaline earth metals ozone however forms
carbonate films [48]. It is possible to get rid of the carbonate by post
deposition annealing but it makes an additional process step and
involves a risk of defect formation. In contrast with the larger alka-
line earth metals, Mg(thd)2 forms quite pure MgO with O3 [22] and
a constant growth rate of 0.27 Å/cycle is observed at 225–250 ◦ C.
A third common oxygen source in ALD is oxygen plasma. SrO and
SrTiO3 have been deposited using Sr(METHD)2 , Ti(Oi Pr)4 and oxy-
gen plasma as precursors and in contrast to the ozone processes
no carbonate was formed. The ALD window was reported also very
wide (150–275 ◦ C) [63]. In one study MgO film was grown from
[Mg2 (thd)4 ] and H2 O2 but with a low rate (0.10–0.15 Å/cycle) and
at relatively high temperatures of 325–425 ◦ C [21].
2.2. Cyclopentadienyl compounds of alkaline earth metals as
precursors for ALD
In Cp compounds the metal is usually coordinated to all five car-
bon atoms in the Cp ring (Fig. 2) and this gives shielding and stability
while still keeping the reactivity. The Cp rings can be substituted to
increase the bulkiness of the ligand and it is also possible to bridge
two rings together to an ansa-compound. Cp compounds are known
for most of the metals and many of them are volatile. Also a large
number of cyclopentadienyl compounds of strontium and barium
have been synthesized and characterized quite well [124,125]. The
Cp compounds of alkaline earth metals (Mg, Ca, Sr, Ba) are very
important in ALD because they enable the growth of oxide films at
reasonable temperatures and growth rates using water as oxygen
source which is very difficult with the alternative thd-precursors.
Cyclopentadienyl compounds have been widely studied start-
ing from the mid-eighties [124] with one of the main motivations
mentioned, in addition to general curiosity, being the possibility
to use these compounds as CVD precursors. However, before 1999
there were only two actual articles reporting usage of cyclopentadi-
enyl compounds of heavier alkaline earth metals as precursors for
CVD [126,127]. In addition to these articles the usage of cyclopen-
tadienyl compounds of strontium and barium in CVD has been
mentioned in several mostly Japanese patents starting as early as
1990 [128]. In contrast, cyclopentadienyl compounds of magne-
sium had been used in CVD more widely starting from at least 1989
[129]. Most obvious reason for the quite low number of reports
is that cyclopentadienyl compounds of alkaline earth metals are
extremely sensitive to air (oxygen) and moisture which makes it
quite difficult to use these compounds in CVD where all the precur-
sors are introduced into the reactor simultaneously. Also for CVD
of thin films containing alkaline earth metals there are many far
more suitable compounds than the cyclopentadienyls, like differ-
ent ␤-diketonates and ␤-ketoiminates which have lower reactivity
and lower thermal stability, often desired in conventional CVD.
In our work we synthesized cyclopentadienyl compounds of
strontium and barium with different cyclopentadienyl ligands and
tested different well known strategies for making them more
volatile and thermally stable i.e. filled the coordination sphere of
the metal centers with multidentate Lewis base molecules, uti-
lized large and sterically demanding cyclopentadienyl ligands to
cover the metal centers, and utilized donor functionalized ligands
(Fig. 2) [65,113,130,131]. Table 3 lists the compounds prepared and
studied.
Most of the as-prepared compounds contained coordinated THF
used as a solvent in the synthesis. After crystallization a fixed
amount (x = 1 or 2) of THF was attached to each molecule. THF
could be removed by sublimation, heating under vacuum or by
using the solvent reflux method. Thus the loosely bonded THF is
lost before or during the evaporation of the compounds and has no
relevant effect on the thermal properties of the compounds. The
isolated compounds were pure as characterized by elemental anal-
ysis, NMR and mass spectroscopy. All MS showed [ML2 ]+ species.
Ions where the neutral solvent or added Lewis base molecule
would have been coordinated to barium were not seen. For the
adducts Ba(Me5 C5 )2 A (A = dien, trien, diglyme, triglyme) this is
in contrast with the results of vacuum sublimation experiments
which resulted in sublimates with composition exactly the same as
before sublimation. Crystal structures were determined for com-
pounds 1, 5, 7, 10, 11, 13 (Fig. 2), 14, 16, 17 (Fig. 2), 18 (Fig. 2)
and 19 [65,113,130–132]. For the others, except the propyl bridged
bis-cyclopentadienyl compounds 8 and 9, and Ba(Me5 C5 )2 (trien)
(12), from which single crystals could not be grown, crystal struc-
tures were already known. All compounds with coordinated Lewis
bases are strictly monomeric. Ba(Me5 C5 )2 is known to form loose
chains where some methyl groups of neighbouring molecules are in
distance of interaction from the barium atom [133]. Similar inter-
actions are found in the structure of Ba(t Bu3 C5 H2 )2 [130]. In the
compounds Ba(Me2 NC2 H4 C5 Me4 )2 (18) and Ba(EtOC2 H4 C5 Me4 )2
(19) the donor atoms O and N are coordinated to the metal center.
Melting point temperatures of the cyclopentadienyl compounds
prepared in general are quite high [113,125]. The lowest melt-
ing temperatures are observed for the compounds with bulkier
ligands i Pr3 C5 H2 − and t Bu3 C5 H2 - , the lowest being 115 ◦ C for
Ba(i Pr3 C5 H2 )2 (THF)2 [132,134]. Most likely the i Pr groups in the
 T. Hatanpää et al. / Coordination Chemistry Reviews 257 (2013) 3297–3322 3301

Table 2
Group II precursors used in ALD.

Metal precursor Other precursor Material deposited Reference

Mg Te MgTe [16,17]

Mg(thd)2 TiF4 TaF5 MgF2 [18,19]

H2 O2 MgF2 [20]
O3 MgO [21]
MgO [22]

Mg(C5 H5 )2 H2 O MgO [23–30]

AlMe3 , O3 MgAl2 O4 [30]

Mg(EtC5 H4 )2 H2 O MgO [31]

Ca(thd)2 H2 O CaO [32]
O3 CaO [33,34]
O3 , (MeO)3 PO, H2 O Ca10 (PO4 )6 (OH)2 [34]
HF CaF2 [35]
TiF4 , TaF5 [18,36]
H2 S CaS [10,37–41]

Ca(i Pr3 C5 H2 )2 H2 O CaO [42]

HfCl4 , H2 O CaO-HfO2

Ca(Tp)2 H2 O CaB2 O4 [43]

Sr(thd)2 HF SrF2 [35]

H2 S SrS [10,38,44–47]
O3 SrO(SrCO3 ) [48]
O3 , Ti(Oi Pr)4 , H2 O SrTiO3 [48,49]
H2 O, Ti(Oi Pr)4 SrTiO3 [50,51]
Ti(Oi Pr)4 , O2 plasma SrTiO3 [52]
H2 O SrO [52–54]
H2 O, Ti(Oi Pr)2 (thd)2 SrTiO3 [55,58]
La(thd)3 , Fe(thd)3 , O3 La1−x Srx FeO3 [59]
Ti(Oi Pr)4 , H2 O plasma SrTiO3 [60,61]
H2 S, Se SrS1−x Sex [62]

Sr(METHD)2 O2 plasma SrO, SrTiO3 [63]

Sr(MTHD)2 O3 SrO [64]
Sr(Me5 C5 )2 H2 S SrS [65]

Sr(n PrMe4 C5 )2 H2 O SrO [66]

La(Me4 C5 H)3 , Mn(Me4 C5 H)2 , H2 O La2 O3 –SrO–MnO [67]

Sr(i Pr3 C5 H2 )2 H2 O SrO [68–72]

O2 SrO [73]
O2 , RuO4 SrRuO3 [73]
O3 SrO [71,74]
O2 plasma SrO [72]
Ti(Oi Pr)4 , H2 O SrTiO3 [4,70,75–77]
H2 O, Ti(Oi Pr)2 (thd)2 , O3 SrTiO3 [78]
Ti(NEtMe)4 , O3 SrTiO3 [79,80]
(Me5 C5 )Ti(OMe)3 , O3 SrTiO3 [74,81]
(MeC5 H4 )2 Hf(OMe)Me, O2 plasma SrHfO3 [72]
H2 S SrS [65,82]

Sr(i Pr3 C5 H2 )2 (DME) (Me5 C5 )Ti(OMe)3 , O2 plasma SrTiO3 [83,85]

H2 O SrO [71]
O3 SrO [71]
(MeCp)Ti(OMe)3 , O3 SrTiO3 [71]
(Me5 C5 )Ti(OMe)3 , O3 SrTiO3 [71]

Sr(t Bu3 C5 H2 )2 H2 O SrO [86,87]

Ti(OMe)4 , H2 O SrTiO3 [86,99]
Ti(OMe)4 , O3 SrTiO3 [100,101]
Ti(Oi Pr)4 , O2 plasma SrTiO3 [102]
(Me5 C5 )Ti(OMe)3 , O3 SrTiO3 [87]
(MeC5 H4 )2 Hf(OMe)Me, H2 O SrO-HfO2 [72]

Sr(Tp)2 H2 O SrB2 O4 [103]

Sr(t But Am2 imidazolato)2 O3 SrO [104]

Sr[Ta(OEt)5 (me)]2 O2 plasma SrTa2 O6 [105]

H2 O [106,107]
3302 T. Hatanpää et al. / Coordination Chemistry Reviews 257 (2013) 3297–3322

Table 2 (Continued )

Metal precursor Other precursor Material deposited Reference

Sr[Ta(OEt)5 (dmae)]2 H2 O SrTa2 O6 [106,107]

O2 plasma [108]
Bi(N(SiMe3 )2 )3 , H2 O Sr–Bi–Ta–O [109]

Ba(thd)2 H2 S BaS [10,110]

Ba(Me5 C5 )2 Ti(Oi Pr)4 , H2 O BaTiO3 [4,75]

H2 S BaS [65,82]

Ba(n PrMe4 C5 )2 Zr(NMe2 )4 , Y(MeC5 H4 )3 , H2 O BaO–ZrO2 –Y2 O3 [111]

Ba(t Bu3 C5 H2 )2 H2 O BaO [75,112]

Ti(Oi Pr)4 , H2 O BaTiO3 [113]
Ti(OMe)4 , H2 O BaTiO3 [112,114]

Ba(TpE t 2 )2 H2 O BaB2 O4 [115]

Ba(t But Am2 imidazolato)2 O3 BaO [104]

Fig. 2. Molecular structures of Ba(Me5 C5 )2 (diglyme), Ba(t Bu3 C5 H2 )2 and Ba(Me4 C5 C2 H4 NMe)2 representing the three different ways to pursue volatility and (thermal)
stability [113,130].

i Pr C H −ligand have freedom to bend and rotate so that the melt-
3 5 2
ing temperature is lowered. Adducts with multidentate Lewis bases
and compounds with donor functionalized Cp ligands had remark-
ably high melting temperatures well above 200 ◦ C.
In order to study the differences in stability and volatility
between the compounds thermogravimetric analyses (TGA) were
carried out under nitrogen atmosphere (Figs. 3–5) as is the com-
mon practice while evaluating ALD and CVD precursors. Typically
a dynamic TGA measurement is done i.e. the temperature of the
sample is increased with a constant heating rate while the weight
of the sample is followed as a function of time and temperature.
A TG curve showing a weight loss in a single step and residue

Table 3
Cyclopentadienyl compounds studied at Laboratory of inorganic Chemistry, Univer-
sity of Helsinki.

Compound Reference

1 Sr(C5 Me5 )2 (THF)2 [65]

2 Sr(i Pr3 C5 H2 )2 (THF) [65]
3 Sr(i Pr3 C5 H2 )2 [132]
4 Sr(t Bu3 C5 H2 )2 (THF) [130]
5 Sr(t Bu3 C5 H2 )2 [130]
6 Sr(C9 H7 )2 (THF)x [131,132]
7 Sr(Me7 C9 )2 (THF)2 [131,132]
8 SrC3 H6 (i PrC5 H3 )2 [131,132]
9 SrC3 H6 (t BuC5 H3 )2 [131,132]
10 Ba(Me5 C5 H)2 (THF)x [65,113]
11–14 Ba(C5 Me5 )2 (A) A = dien, trien, diglyme, triglyme [113]
15 Ba(i Pr3 C5 H2 )2 (THF)2 [132]
16 Ba(t Bu3 C5 H2 )2 (THF) [113]
17 Ba(t Bu3 C5 H2 )2 [130]
18 Ba(Me2 NC2 H4 C5 Me4 )2 [113]
19 Ba(EtOC2 H4 C5 Me4 )2 [113]
Fig. 3. TG curves of cyclopentadienyl compounds of strontium. Flowing 1 atm N2
20 Ca(i Pr3 C5 H2 )2 (THF)2 [42]
atmosphere, 10 ◦ C/min, ∼10 mg samples.
 T. Hatanpää et al. / Coordination Chemistry Reviews 257 (2013) 3297–3322
Fig. 4. TG curves of cyclopentadienyl compounds of barium with donor function-
alized ligands and Me5 C5 ligands + ancillary Lewis base ligands. Flowing 1 atm N2
atmosphere, 10 ◦ C/min, ∼10 mg samples.
close to zero indicates a good volatility and thermal stability. TGA
gives information of thermal stability of a compound studied only
in the condensed state, not in the gas phase. Therefore when the
compound studied is highly volatile and there is no or very little
residue after the measurement it can only be said that the com-
pound is thermally stable at least up to the temperature where the
evaporation process was complete. Larger residues indicate decom-
position of the samples. Multiple steps indicate dissociation or
decomposition of the compounds studied, like dissociation of neu-
tral adduct ligands at lower temperature followed by evaporation
of the main compound at higher temperature, or decomposition of
the precursor compound into a stable and non-volatile solid. Those
complexes which have protecting, sterically demanding ligands,
like i Pr3 C5 H2 − and t Bu3 C5 H2 − (2–5, 15–17) were found to evap-
orate and leave residues below 8%. Compounds Sr(Me5 C5 )2 (THF)x
and Sr(Me5 C5 )2 (THF)x (x = 0–2) left 18 and 37% residues, respec-
tively, indicating some decomposition. Under vacuum the above
mentioned compounds 1–5, 10 and 15–17 sublimed at 110–220 ◦ C
with a loss of possibly coordinated THF solvent. All the other com-
plexes, i.e. those having pentamethyl substituted Cp + multidentate
Lewis base ligand (11–14), indenyl (6, 7), N and O functionalized Cp
(18, 19) or ansa ligands (8, 9) seemed mainly to decompose in the
Fig. 5. TGA curves of Ba(Me5 C5 )2 (THF)2 Ba(i Pr3 C5 H2 )2 (THF)2 and
Ba(t Bu3 C5 H2 )2 (THF). Inset shows TGA curves measured for Lewis base free
Sr(t Bu3 C5 H2 )2 and Ba(t Bu3 C5 H2 )2 . Flowing 1 atm N2 atmosphere, 10 ◦ C/min,
∼10 mg samples.
3303
TG measurements leaving 30–70% residues. To make any conclu-
sions what are the decomposition paths is quite impossible. Clearly
adding multidentate Lewis bases to Ba(Me5 C5 )2 (11–14) did not
enhance but lowered the volatility as compared to the Lewis base
free Ba(Me5 C5 )2 or the THF adduct (Fig. 4). Also the thermal stability
was not enhanced. This was also confirmed by vacuum sublimation
experiments: vacuum sublimation of the adducts 11–14 required
higher temperatures (180–260 ◦ C) than pure Ba(Me5 C5 )2 and also
the sublimation yields were low (for 11 63% and for 12–14 32–39%)
though it seems that the compounds sublimed intact as the subli-
mates were found to be identical with the unsublimed compounds.
Noticeable is that TGA showed Ba(Me2 NC2 H4 C5 Me4 )2 (18) to be
stable up to ca 290 ◦ C above which it decomposes rapidly. Under
vacuum Ba(Me2 NC2 H4 C5 Me4 )2 (18), however, showed very good
sublimation behavior at 200–260 ◦ C.
In conclusion the best approach for making volatile and ther-
mally stable cyclopentadienyl compounds of Sr and Ba was
definitely the usage of large and sterically demanding cyclopenta-
dienyl ligands. The i Pr3 C5 H2 − and t Bu3 C5 H2 − ligands were found to
make a good match with Sr and Ba. With similar ligands the thermal
properties of Sr and Ba compounds are very similar. Inset in Fig. 5
shows TG curves measured for Sr(t Bu3 C5 H2 )2 and Ba(t Bu3 C5 H2 )2 .
It seems likely that i Pr4 C5 H2 − and (Me3 Si)3 C5 H2 − ligands could
be equally good [135,136] but extremely crowded ligand i Pr5 C5 −
[137] may be even too bulky for Sr and Ba in the sense that
the reactivity with H2 O is lowered. However, making the tetra
and pentaisopropyl substituted cyclopentadienyl ligands is more
complicated compared to the trisubstituted ligands [135,137].
Adducting the cyclopentadienyl compounds or using donorfunc-
tionalized cyclopentadienyl ligands was found not to be beneficial.
Volatilities or thermal stabilities of adduct compounds were not
enhanced if compared to the Lewis base free compounds.
In general cyclopentadienyl compounds of alkaline earth metals
have been used especially in ALD of oxides of Mg, Ca, Sr and Ba
but also sulfides of strontium and barium have been deposited
(Table 2). The advantages of the cyclopentadienyl compounds over
the ␤-diketonates are high reactivity against oxygen precursors and
higher thermal stability. Oxygen precursors used with cyclopenta-
dienyls are H2 O, O3 and oxygen plasma. Unlike the ␤-diketonates of
Sr and Ba, the cyclopentadienyl compounds form sufficiently pure
Sr and Ba containing films with all three oxygen precursors.
SrS and BaS were deposited using Sr(Me2 C5 )2 , Ba(Me5 C5 )2 and
Sr(i Pr3 C5 H2 )2 as metal precursors and H2 S as a sulfur precursor
[65,82]. Growth rates of the processes at different temperatures
are shown in Fig. 6. Typical ALD window was observed for all
Fig. 6. Growth rate of SrS and BaS thin films as a function of the deposition tempera-
ture. At 120 ◦ C, a pulse length of 1.5 s was used with complex 1 to ensure its uniform
distribution across the substrate [65]. Reprinted with permission from Chem. Mater.
14 (2002) 1937. Copyright 2002 American Chemical Society.
3304 T. Hatanpää et al. / Coordination Chemistry Reviews 257 (2013) 3297–3322
three processes. As can be seen from the figure, the temperature
where the growth rate starts to increase is lower when Sr(Me5 C5 )2
(>350 ◦ C) and Ba(Me5 C5 )2 (>300 ◦ C) are used as precursors as
compared to Sr(i Pr3 C5 H2 )2 (>380 ◦ C) [82]. The increase of the
growth rate at high temperatures is associated to a decomposi-
tion of the precursors. The temperature independent growth rates
under the self-limiting conditions observed for the three precur-
sors follow the order Ba(Me5 C5 )2 > Sr(Me5 C5 )2 > Sr(i Pr3 C5 H2 )2 as
expected: Ba is a larger cation than Sr, and i Pr3 C5 H2 is a larger
ligand than Me5 C5 requiring larger surface area in the saturatively
formed monolayer of the precursor on the surface of the growing
film. The sulfide films deposited were all polycrystalline. Impu-
rity levels in the films deposited at 300 ◦ C were low (C 0.1 at.%, H
0.3–0.5 at.%, O 0.3–0.6 at.%). When compared with the previous SrS
and BaS processes using the thd compounds and H2 S, the usage
of the Cp compounds allowed lower deposition temperatures as
lower evaporation temperatures could be used. The Cp compounds
also resulted in higher or similar growth rates, depending on the
temperature, as the thd compounds. Roughnesses of the SrS films
grown using the Cp compounds of strontium were also lower.
We have studied cyclopentadienyl compounds for both binary
and ternary oxides of the larger alkaline earth metals. Oxide
materials deposited have been CaO, SrO, BaO, SrTiO3 , BaTiO3 and
Ba1−x Srx TiO3 . In all the processes H2 O was used as the oxygen pre-
cursor. Water is a difficult precursor for the binary oxides of the
larger alkaline earth metals because of the easy formation of metal
hydroxide [112]. The hydroxide formation and the reverse reaction
of dehydration back to the oxide are strongly dependent on the
process temperature and can greatly complicate the ALD growth
characteristics of the binary oxides. Fortunately in the far more
important ternary oxides, such as SrTiO3 and BaTiO3 , the hydra-
tion/dehydration processes are effectively stopped by the presence
of the other metal oxide [70,112].
The binary oxides of Ca, Sr and Ba are not important materials
due to their high reactivity in ambient atmosphere. However, SrO
and BaO growth experiments were carried out in order to study the
absorption of H2 O in the growing films [70,112]. The precursors
used were Ba(t Bu3 C5 H2 )2 , Sr(i Pr3 C5 H2 )2 and Sr(t Bu3 C5 H2 )2 . It is
known that especially BaO is very keen in absorbing large amounts
H2 O and forming Ba(OH)2 (H2 O)n which could interfere the growth
of Ba oxide materials. It was found that at 250–340 ◦ C the growth
chemistry of BaO is significantly influenced by the H2 O absorp-
tion. The amount of H2 O absorbed decreases with increasing H2 O
purge times and growth temperature. Up to 290 ◦ C the films were
Ba(OH)2 . At 340 ◦ C there was still some Ba(OH)2 in the films. SrO
has a slightly lower reactivity towards H2 O than BaO and it proved
to be much easier to grow uniform SrO films. At 300 ◦ C the growth
rates were 0.42 and 0.28 Å/cycle for processes using Sr(i Pr3 C5 H2 )2
and Sr(t Bu3 C5 H2 )2 , respectively. At this temperature the films were
crystalline (1 1 1) oriented SrO. With calcium there is much less
problems with hydration. CaO was deposited using Ca(i Pr3 C5 H2 )2
and H2 O. At 300 ◦ C the growth rate was around 1 Å/cycle [42].
Finally, MgCp2 is a good precursor for ALD of MgO films. Constant
growth rate of 1.16 Å/cycle could be achieved with the MgCp2 –H2 O
process at 200–300 ◦ C as reported by Putkonen et al. [26].
For SrTiO3 two sets of precursors were used: Sr(i Pr3 C5 H2 )2 ,
Ti(Oi Pr)4 , H2 O [4,76], and Sr(t Bu3 C5 H2 )2 , Ti(OMe)4 and H2 O [70].
With the first set temperature range of 250–325 ◦ C was studied.
The growth was the most ideal at 250 ◦ C giving highly uniform but
mostly amorphous films with a growth rate of 0.5 Å/cycle. At 325 ◦ C
which is already above the decomposition limit of Ti(Oi Pr)4 the
SrTiO3 films began to crystallize during the growth when exceed-
ing approx. 50 nm thickness, first with random orientation and
then in preferred (1 0 0) orientation. High water doses resulting
in Sr(OH)2 formation enhanced the crystallization and also the
substrates had an effect. On crystalline platinum the films were
crystalline whereas on amorphous Al2 O3 they were amorphous
[70]. When SrTiO3 was deposited on an MBE-grown seed layer
at 325 ◦ C the film grew epitaxially and no interface between the
MBE and ALD layers could be seen with HRTEM (Fig. 7). To deposit
stoichiometric SrTiO3 a cycling ratio of 5:6 (Sr/Ti) was found to be
appropriate.
With the second set of thermally more stable precursors
Sr(t Bu3 C5 H2 )2 and Ti(OMe)4 , SrTiO3 was grown at 300 ◦ C [70]. With
the 1:1 Sr:Ti cycling ratio a self-limiting growth rate of 0.4 Å/cycle
and a Sr:Ti ratio of 3:7 in the film were achieved. The 2:1 cycling
ratio was found to result in slightly Sr rich films but reaching the
saturation was found to be more complicated and an increase in the
growth rate was observed. The average surface composition during
the Sr–O cycle clearly influences the growth behaviour [70]. Surface
composition effecting the growth behaviour seems to be a general
feature in ALD of ternary compounds.
Dielectric properties of the SrTiO3 films prepared were tested in
MIM capacitors. A 490 nm film grown at 325 ◦ C using Sr(i Pr3 C5 H2 )2 ,
Ti(Oi Pr)4 and H2 O had a permittivity of 130 after annealing in air at
500 ◦ C. A 49 nm film grown at 300 ◦ C using Sr(t Bu3 C5 H2 )2 , Ti(OMe)4
and H2 O and annealed at 750 ◦ C had a permittivity of 90 at 1 V,
resulting in EOT of 2.2 nm. Leakage currents of <50 nm films were
fairly high, above 10−5 A/cm2 at 1 V [70].
Deposition of BaTiO3 was tested with three sets of precursors:
Ba(Me3 C5 )2 , Ti(Oi Pr)4 and H2 O [4], Ba(t Bu3 C5 H2 )2 , Ti(Oi Pr)4 and
H2 O [113], and Ba(t Bu3 C5 H2 )2 , Ti(OMe)4 and H2 O [112]. The first
set resulted in reasonably uniform films up to deposition temper-
atures of 275 ◦ C. With the second set crystalline BaTiO3 films were
grown at 350 ◦ C with 1.0 Å/cycle growth rate. The high growth
rate observed in this preliminary study was associated to Ti(Oi Pr)4
decomposition and formation of barium hydroxide as an inter-
mediate. At 250 ◦ C the process was difficult to control due to the
enhanced hydroxide formation at this temperature. Purge times
after water and barium precursor pulses strongly affected the
growth rates but still uniform films could be deposited with fixed
pulse lengths and long purge times after water. With the third
precursor set using Ti(OMe)4 instead of Ti(Oi Pr)4 higher process
temperatures could be used and self-limiting growth conditions
were found [112]. Films grown from Ba(t Bu3 C5 H2 )2 and Ti(OMe)4
at 340 ◦ C with a 1:1 pulsing ratio showed a Ba/Ti ratio of 0.56 in
the film. With a pulsing ratio 2:1 the stoichiometry of the film
improved to a Ba/Ti ratio of 1.05. Growth rates ranged from 0.37 and
to 0.50 Å/cycle. MIM capacitors annealed at 800 ◦ C with platinum
electrodes and 140 nm thick BaTiO3 films showed permittivity of
280 and EOT below 2 nm.
ALD also allows the deposition of Ba1-x Srx TiO3 (BST) films of dif-
ferent composition simply by changing the Ba/Sr pulsing ratio. BST
films were deposited at 300 ◦ C using Sr(t Bu3 C5 H2 )2 , Ba(t Bu3 C5 H2 )2 ,
Ti(OMe)4 and H2 O as the precursors [70]. With a 1:1:1 Ba:Sr:Ti puls-
ing ratio the (Ba + Sr):Ti ratio was close to 1 but the Ba:Sr ratio varied
from 1.30:1 to 1.52:1 depending on the Ba precursor dose. In MIM
structures with Pt electrodes, after 2 min annealing at 750 ◦ C, 35 nm
BST layers showed a permittivity of 135, an EOT of 1.08 nm, and a
leakage current density of 1 × 10−5 A/cm2 at 1 V.
After the initial research on ALD of SrTiO3 and BaTiO3 with
small scale research reactor the processes were scaled-up to
larger reactors in co-operation with ASM Microchemistry [70,114].
While depositing SrTiO3 on larger substrates using Sr(i Pr3 C5 H2 )2 ,
Ti(Oi Pr)4 and H2 O the process temperature was limited to 250 ◦ C
due to the limited thermal stability of Ti(Oi Pr)4 that is more
readily observed on large substrates. Anyway films of uniform
composition and thickness could be grown on 30 cm × 40 cm
glass substrates [70]. Soon after the process with the improved
Ti and Sr precursors Ti(OMe)4 and Sr(t Bu3 C5 H2 )2 was adapted
by ASM Microchemistry for ALD of SrTiO3 on up to 300 mm
wafers. The BaTiO3 process using Ba(t Bu3 C5 H2 )2 , Ti(OMe)4 and
 T. Hatanpää et al. / Coordination Chemistry Reviews 257 (2013) 3297–3322
Fig. 7. HRTEM images showing the influence of an epitaxial MBE seed layer on ALD growth. A SiO2 layer which forms during the processing is seen between Si and the
epitaxial SrTiO3 [70].
H2 O was first scaled up on 200 mm silicon wafers [114]. Later
these processes have been extensively studied at IMEC for device
integration [86–99].
The reactivity of the Sr and Ba Cp compounds with water is
high and from that point of view there is no need for other oxygen
precursors [4,86]. But as noted, with water the hydroxide forma-
tion may cause complications. In addition, slow purging of water
especially from large batch reactors with high surface areas has
made industry to prefer ozone as an alternative oxygen precur-
sor. STO films can be grown with ozone but the state-of-the-art
Sr-rich ALD STO films which show EOT < 0.5 nm with low leak-
age (10−7 A/cm2 ) at 1 V have been made with water using the
Sr(t Bu3 C5 H2 )2 –H2 O–Ti(OMe)4 –H2 O process at 250 ◦ C followed by
annealing at 600 ◦ C [88,92]. The structure of the MIM capacitor was
Ru/RuOx /Sr rich STO/TiN. The RuOx /STO interface may also contain
rutile TiO2 . Both RuOx and rutile TiO2 are beneficial surfaces for
ALD of STO. They help the crystallization of the STO film thereby
minimizing the “dead-layer” in STO. In addition TiO2 may increase
the Ti content in STO films and RuOx can heal traps associated to
oxygen vacancies by releasing oxygen during annealing with the
both processes decreasing the leakage current density.
3. Group 4 elements
Oxides of the group 4 metals form one of the most studied mate-
rials group in ALD. The interest towards ZrO2 and HfO2 stems from
their good dielectric properties. ALD HfO2 is used industrially as a
high-k gate oxide in MOSFET transistors [138] and ALD ZrO2 as a
dielectric material in DRAM capacitors [139]. The high aspect ratios
in DRAMs and also the need to decrease the leakage current by mak-
ing ZrO2 –Al2 O3 –ZrO2 nanolaminates call for the use of ALD in the
thin film processing. TiO2 is a versatile material which also has a
high dielectric constant especially in rutile form but is not used
as a dielectric material because of the problems of high leakage
currents. TiO2 films find applications as photocatalysts, protective
coatings, and as a component in titanates and mixed oxide and
nanolaminates such as Alx Tiy Oz (ATO) that is used commercially in
the electroluminescent displays. Group 4 metal oxides have several
crystal structures with properties of their own. Therefore in thin
film deposition besides the composition and purity also the forma-
tion of the desired crystal structure is important. In case of TiO2
the anatase form is preferred in photocatalysts, and the rutile form
when a high-k value is needed. ZrO2 and HfO2 have monoclinic,
3305
tetragonal and cubic forms from which the last ones are desired in
high-k applications.
The recent development in Ti precursors for ALD aims at the
desired properties mentioned above: high reactivity, good thermal
stability, preferably liquid at room temperature, and good compat-
ibility with Sr(R3 C5 H2 )2 precursors for deposition of SrTiO3 . The
latest complexes are heteroleptic following the idea that one of the
ligands gives reactivity and the other thermal stability.
3.1. Group 4 metal halides as precursors for ALD
Chlorides of group 4 metals are very important precursors since
they are volatile, stable, cheap and highly reactive with water. The
chloride ALD process for all these oxides has been known for over
20 years [1,2,140]. Chlorides have certain drawbacks such as ZrCl4
and HfCl4 are solids, the reaction by-product is corrosive HCl, and
incompatibility with some other film constituents like strontium in
SrTiO3 that readily forms SrCl2 . The problem of being solid and pos-
sibly causing particle problems has been overcome and HfCl4 , for
example is used in industrial scale [141]. TiCl4 is extensively used
ALD precursor when cheap, easily delivered precursor is needed [5].
From the other halides iodides have been in some extent studied
as possible precursors for the TiO2 , ZrO2 and HfO2 films [142,143].
The chloride–water process works at a wide temperature range:
from room temperature (with the highly volatile TiCl4 ) to at least
750 ◦ C. As mentioned above, in the growth of ZrO2 films for the
high-k applications the crystal structure formed is important. The
most stable phase is the monoclinic one but its k-value is only
around 20 while the tetragonal and cubic phases have values of
30–40. The ZrCl4 –H2 O process produces amorphous films below
210 ◦ C, tetragonal at 210–300 ◦ C, and a mixture of tetragonal and
monoclinic at higher temperatures. Interestingly the k-values of
the films remained rather low (around 20) despite the crystal
structure [144]. HfCl4 –H2 O process on the other hand, produces
mainly monoclinic phase which also shows k-value close to 20
[145]. With decreasing film thickness the fraction of the tetragonal
phase increases, however, as observed in for example HfO2 –Ta2 O5
nanolaminates [145].
Metal chlorides react also with metal alkoxides producing either
a binary oxide or mixed oxide depending on whether the metals in
the two precursors are the same or different, respectively [146]. The
byproduct of this reaction is alkylchloride [147]. Because no sep-
arate oxygen precursor is used, and oxygen is bound to a metal
3306 T. Hatanpää et al. / Coordination Chemistry Reviews 257 (2013) 3297–3322

Fig. 8. Thermal decomposition of Ti(OMe)4 , Ti(OEt)4 , Ti(Oi Pr)4 and Ti(Ot Bu)4 . ALD
equipment with in situ QMS was used to produce the data. The amount of decom-
position was determined by dividing the main fragment of the ligand by a precursor
fragment [149].
with high oxygen affinity, the process oxidises the substrate or
underlying film less than the normal oxide ALD processes.
Fig. 9. Crystal structure of [Zr(Ot Bu)2 (dmae)2 ]2 dimer [154]. Reproduced with a
permission from J. Non-Cryst. Solids 303 (2002) 24. Copyright 2002, Elsevier.
ligand dmae (dmae = dimethylaminoethoxide) (Fig. 9) allowed to
increase slightly the deposition temperature but thermal decompo-
sition of the metal precursor was anyway seen in the experiments
[154]. The situation was similar when − Ot Bu ligand was changed to
− Oi Pr or a complete homoleptic dimethylaminoethoxide complex,

3.2. Group 4 alkoxides as precursors for ALD Zr(dmae)4 , was used [155]. The monomeric heteroleptic alkoxide
Hf(Ot Bu)2 (mmp)2 with tertiary mmp ligand (mmp = 1-methoxy-2-
Metal alkoxides are common precursors in CVD of oxide films. methyl-2-propanolate) (Fig. 10) [156] showed rather good thermal
In ALD simple titanium alkoxides (OMe, OEt, i OPr, t OBu) have been stability up to 275 ◦ C but at these temperatures the reactions with
widely studied and used with water to deposit TiO2 . Alkoxides of water remain incomplete resulting in low growth rate and high
Zr and Hf, by contrast, have been much less used in ALD because residue contents [157]. Fairly homogeneous films could be grown
of their lower thermal stability compared to the Ti alkoxides. The at 240 ◦ C but at 340 ◦ C some decomposition occurred which could
smaller alkoxides tend to oligomerize and the oligomerization also be seen in the increase of the growth rate from 0.58 Å at 240 ◦ C
depends on the metal increasing in the order Ti < Zr ≈ Hf. On the to 1.48 Å/cycle at 340 ◦ C. The homoleptic Hf(mmp)4 behaved quite
other hand, the stability of the alkoxides decreases in a series similarly [158]. A homoleptic hydroxylamide Hf(ONEt2 )4 , when
OMe > OEt > Oi Pr > Ot Bu which has been best confirmed with tita- used together with water, showed a narrow growth temperature
nium (Fig. 8) [148,149]. Monomolecular complexes are formed only range with the optimum being 300 ◦ C where reasonably good sat-
with iso-propoxy and t-butoxy ligands. uration at 0.5 Å/cycle was achieved [159]. The films were quite
TiO2 with anatase structure can be grown from titanium alkox- severely contaminated with hydrogen (11 at.%) and carbon (6 at.%),
ides and water between 225 and 350 ◦ C. Because of thermal however, while the nitrogen content was below 0.1 at.%. At 250 ◦ C
decomposition of the alkoxides, the maximum temperatures with the growth was weak, showing that the bidentate hydroxylamide
the titanium ethoxide and i-propoxide are about 325 ◦ C while the
methoxide allows the use of 350 ◦ C [148,149]. Close to the decom-
position onset temperature however the decomposition is so slow
that the films are still reasonably uniform and a linear depend-
ence of film thickness on the number of deposition cycles is valid
[150,151]. The growth rate per cycle follows inversely the size of
the precursor being the highest with the smallest methoxide ligand
that gives a rate of 0.65 Å/cycle at 350 ◦ C.
Polycrystalline ZrO2 films can be grown from Zr(Ot Bu)4 and
water at 200–300 ◦ C. The growth rate decreased strongly when
the temperature was increased from 200 to 300 ◦ C. On the other
hand, the growth rate increased with higher precursor doses
and longer pulse times indicating decomposition of Zr(Ot Bu)4 .
However, the polycrystalline films showed a high-k value of 32
indicating tetragonal or cubic structure [152]. Hf(Ot Bu)4 is also an
extremely air and moisture sensitive compound and as difficult to
use in ALD [153].
The poor thermal stability of zirconium and hafnium alkoxides
has been tried to be improved by using ligands that have been donor
functionalized by amine or ether groups. These have been used both
in homoleptic and heteroleptic complexes but with a general con-
clusion that thermal stability and high reactivity with water cannot
be achieved at the same time because coordinative saturation that
Fig. 10. Crystal structure of M(Ot Bu)2 (mmp)2 (M = Zr, Hf) [156]. Reproduced with a
improves stability also decreases reactivity. The use of a dimeric permission from Chem. Vap. Deposition 8 (2002) 163. Copyright 2002, John Wiley
heteroleptic precursor [Zr(Ot Bu)2 (dmae)2 ]2 with primary alkoxy and Sons.
 T. Hatanpää et al. / Coordination Chemistry Reviews 257 (2013) 3297–3322 3307

ligands shield hafnium more effectively than the related monoden-

tate –NR2 and –OR ligands.

3.3. Group 4 alkylamides as precursors for ALD

Alkylamides form another important group of precursors for the

group 4 metals. The homoleptic tetrakis complexes used in ALD
usually contain dimethyl-, ethylmethyl- or diethyl-substituents at
the nitrogen. Especially for zirconium the ethylmethylamide is
widely used in oxide depositions. Alkylamides have several advan-
tages: easy synthesis, high reactivity with water, relatively small
molecules resulting in growth rates about 1 Å/cycle. Besides oxide
films alkylamides have been studied as precursors for nitride com-
bined in thermal processes with ammonia or in plasma processes
with ammonia, nitrogen or hydrogen plasma [5].
Thermal stability of alkylamides of group 4 metals shows a
reverse order compared to alkoxides: titanium alkylamides are less
stable than the corresponding zirconium and hafnium complexes.
Fig. 11. Growth rate of HfO2 films as a function of deposition temperature. Precur-
Thermal decomposition of Ti(NMe2 )4 has been reported to start at sors Cp2 HfMe2 and water. The inset shows the growth rate at 350◦ as a function of
180 ◦ C [160]. TiO2 films have been grown from this precursor and the Cp2 HfMe2 pulse length [173]. Reproduced by permission of The Royal Society
the growth rate is high at low temperatures (<100 ◦ C) and decreases of Chemistry.
strongly towards 325 ◦ C [161]. Hausmann et al. [162] reported
much higher temperatures for zirconium and hafnium, the max-
reactions with the surface –OH groups (Fig. 12) [174]. This is in
imum deposition temperatures being for Zr(NMe2 )4 , Zr(NMeEt)4 ,
line with the expected bonding strength of the ligands. The poly-
and Zr(NEt2 )4 250, 300 and 350 ◦ C, and for Hf(NMe2 )4 , Hf(NMeEt)4 ,
crystalline films of HfO2 show monoclinic structure while ZrO2
and Hf(NEt2 )4 350, 400 and 450 ◦ C, respectively. It seems that the
forms mixed phases. Thus, the presence of the low permittivity
decomposition temperature depends on the reactor design since in
monoclinic phase in ZrO2 has an effect on CET values which were
our reactors decomposition is seen already at the above mentioned
>1 nm.
temperatures. For example, with Zr(NMeEt)4 there is a growth rate
Cp compounds of the group 4 metals are usually solids. Indus-
difference between 275 and 300 ◦ C [163]. Low decomposition tem-
try prefers liquid source materials and the tuning of the precursor
peratures have also been observed for Hf(NMeEt)4 in batch reactors
molecules to liquid at room temperature is one of the driving forces
[164].
in the precursor development. In bis-Cp compounds such a small
Good results have been reported for ZrO2 films grown from
variation in structure as a change of one methyl ligand to a methoxy
Zr(NMeEt)4 and water or ozone. It is possible to reach permittivity
ligand lowered the melting point below room temperature. The
values close to 40 which is a sign of tetragonal or cubic structure
studied (CpMe)2 Zr(OMe)Me compound showed similar thermal
[165]. This can lead to CET values as low as 0.8 nm [166]. Hf(NMe2 )4
stability as the bis-methyl compounds [175]. The methoxy substi-
and Hf(NMeEt)4 precursors behave differently. The oxide films
tuted compound improved slightly also the other weak property of
deposited from them with water show predominantly monoclinic
Cp compounds, viz. low growth rate which increased by 0.1 Å/cycle.
structure and permittivity values less than 20 [167,168]. This seems
The reaction mechanism studies showed that methyl and methoxy
to be more the property of hafnium oxide. High-k value forms of
groups are mainly removed during the metal precursor pulse and
HfO2 can be achieved by doping the films for example with rare
the CpMe ligand during water/ozone pulse [176]. XRD measure-
earth ions. Good results have been reported for HfO2 doped with
ments showed that the ZrO2 films formed contained mixed phases
7% of yttrium [169]. Although with ZrO2 it is easier to the tetrago-
and permittivity value remained quite low, however.
nal or cubic form than with HfO2 doping ZrO2 with for example
strontium assists in formation of these high permittivity phases
[170]. 3.4.2. Mono-cyclopentadienyl compounds
As described above, the Cp-precursors offer good thermal sta-
3.4. Group 4 Cyclopentadienyl compounds for ALD bility but modest growth rate and tendency to form films with a
mixture of oxide phases. Zirconium alkylamides, on the other hand
3.4.1. Bis-cyclopentadienyl compounds show higher volatility and growth rate but suffer from thermal
Bis-cyclopentadienyl (Cp) compounds represent true instability. Films grown from alkylamides show in addition better
organometallic compounds used as precursors for group 4 phase outcome where the high permittivity tetragonal and cubic
metal oxides. Two Cp rings coordinate in ␩5 fashion to the metal phases are dominating. In mixed ligand complexes (CpR)Zr(NMe2 )3
and the other two ligands usually are either chlorides or methyl (R = H, Me or Et) the benefits of the both precursor types can be
groups. The bis-cyclopentadienyl compounds react rapidly with combined [177]. Pure, conformal films (Fig. 13) were grown by an
both water and ozone and resulting oxide material is very pure. ozone process with a growth rate close to 1 Å/cycle. No signs of pre-
The thermal stability of the bis-Cp compounds is higher than that cursor decomposition were seen at 300 ◦ C. A CET value of 0.7 nm
of alkoxides and alkylamides and deposition temperatures > 300 ◦ C with targeted low leakage current density was measured from a
are achievable for ZrO2 and HfO2 [170]. Cp compounds of titanium MIM capacitor with 6 nm ZrO2 film. When the similar cyclopenta-
have only sparsely been studied in ALD. dienyl and alkylamido ligands were applied to hafnium the results
The ALD of both ZrO2 and HfO2 has been studied using dif- were not as good as with zirconium. HfO2 films grew in the
ferent bis-Cp compounds and both water and ozone as oxygen (CpR)Hf(NMe2 )3 –O3 process with a rate of 0.8 Å/cycle but the films
precursors [171–173]. The growth rate is typically 0.5–0.6 Å/cycle contained mixed phases with the monoclinic phase being dominant
(Fig. 11). The in situ reaction mechanism studies showed that in [178]. The as-deposited thin films (<10 nm) were amorphous but
the Cp2 Zr(CH3 )2 –water process 90% of methyl groups and 40% after annealing they contained mixed phases. Only yttrium doped
of Cp groups were released during the metal precursor pulse in films showed high permittivity structures.
3308 T. Hatanpää et al. / Coordination Chemistry Reviews 257 (2013) 3297–3322
Fig. 12. Surface reactions in the Cp2 ZrMe2 /D2 O ALD process at 350 ◦ C as proposed
based on in situ studies with QMS and QCM. Upon adsorption of Cp2 ZrMe2 more
methyl than Cp ligands are released in exchange reactions with the surface –OD
groups (b). The following D2 O pulse releases the rest of the ligands as MeD and CpD
releasedconverts the surface back to OD-terminated [174]. Reprinted with permis-
sion from Langmuir 21 (2005) 7321. Copyright 2005 American Chemical Society.
Mixed ligand complex (Me5 C5 )Ti(OMe)3 has been found to be
thermally highly stable[179–181] but unfortunately they lack reac-
tivity against water and more powerful oxidizers like O3 have to be
used. Initial ALD investigations revealed a very wide ALD process
window with deposition temperatures up to 375–400 ◦ C [179,180].
Rose et al. [181] found that at 260–330 ◦ C the growth rate increased
slowly from 0.22 to 0.29 Å/cycle and then raised up to 0.50 Å/cycle
at 350 ◦ C. The density of films was the highest at 330 ◦ C and dropped
significantly at 350 ◦ C. However, the growth was still linear at
350 ◦ C. SrTiO3 was deposited at 250 and 300 ◦ C using Sr(i Pr3 C5 H2 )2 ,
(Me5 C5 )Ti(OMe)3 and O3 as precursors [81]. Films grown at 300 ◦ C
using SrO:TiO2 cycle sequences of 10:10 and 5:5 both possessed a
Sr/Ti atomic ratio of 0.90. The films grown at 300 ◦ C and crystal-
lized by annealing had high leakage while films grown at 250 ◦ C
had much lower leakage.
3.5. Other group 4 precursors for ALD
Low thermal stability of titanium complexes has been a con-
cern especially in deposition of SrTiO3 films where it is desired
that the films grow directly into the crystalline form. Com-
pounds aimed to solve this have been e.g. the above mentioned
Fig. 13. Cross-sectional SEM images of a ZrO2 film grown by the CpZr(NMe2 )3 /O3
process at 275 ◦ C into 60:1 aspect ratio trenches. The upper image shows the top
part of the trench, those below the middle and bottom parts. The trench open-
ing is 115 nm and depth 6.75 mm. Labels denote the ZrO2 film thicknesses [177].
Reproduced by permission of The Royal Society of Chemistry.
(Me5 C5 )Ti(OMe)3 and Ti(i OPr)2 (thd)2 [55–57,71,79,81,83–85,87].
Interestingly the recent approach to use heteroleptic alkylamido-
alkoxo and acetamidinato-alkoxo complexes also improved the
thermal stability although the homoleptic parent compounds
show low thermal stability [182]. TiO2 films can be grown from
Ti(NMe2 )2 (Oi Pr)2 and Ti(i PrNCHNi Pr)(Oi Pr)3 together with water
in a controlled way up to 350 ◦ C with a rates of 0.75 and 0.45 Å/cycle.
Yet another approach to use heteroleptic complexes involves
a combination of cyclopentadienyl and cycloheptatrienyl
(CHT = C7 H7 ) ligands (Fig. 14) [183]. These complexes have
been synthesized for Ti and Zr. The compounds are thermally very
stable and growth temperatures exceeding 400 ◦ C are possible.
The oxide growth requires the use of ozone and growth rates of
0.7–0.8 Å/cycle have been recorded. In ZrO2 films the high permit-
tivity phases are dominating and accordingly low CET values were
 T. Hatanpää et al. / Coordination Chemistry Reviews 257 (2013) 3297–3322 3309

Fig. 15. Molecular structure of (t BuMe2 Si)2 Te [3]. Reproduced with permission from
J. Am. Chem. Soc. 131 (2009) 3478. Copyright 2009 American Chemical Society.

harmful level. By contrast, the hydrides of selenium and tellurium

are much more dangerous and would require extensive safety sys-
tems and exhaust gas treatment. Alkyl compounds of selenium and
tellurium have been quite widely used in CVD but in ALD they do
not provide efficient exchange reactions with the common metal
precursors. In group 15 there is similar trend: NH3 can be used with
appropriate precautions while PH3 , AsH3 and SbH3 are much more
dangerous gases.

4.1. Alkylsilyl compounds of group 15 and 16 elements

A breakthrough in ALD of GST and related materials, including

selenides, was made when alkylsilyl compounds (R3 Si)2 M (M = Te,
Se) were identified as efficient ALD precursors with good volatility,
thermal stability and high reactivity [3]. Soon after, it was also real-
ized that alkylsilyl compounds of group 15 elements have similar
properties [187,188]. Fig. 15 shows the structure of (t BuMe2 Si)2 Te
and Fig. 16 TG curves measured for a set of group 15 and 16 alkylsi-
lyl compounds. TGA measurements reveal that all compounds of
Fig. 14. Molecular structure of (MeCp)Zr(C7 H7 ) (above) and TG curves measured the group 16 elements are volatile and they exhibit pure evap-
for CpTi(C7 H7 ) and (MeCp)Zr(C7 H7 ) [183]. Reprinted with permission from Chem.
Mater. 24 (2012) 2002. Copyright 2012 American Chemical Society.
oration behavior. Their thermal stability also seems to be good.
Volatility of the compounds depends strongly on their molecular
reported. TiO2 films on the other hand showed anatase structure weight. Compounds of group 15 elements lose weight at higher
at low temperature (250 ◦ C), rutile structure at high temperatures temperatures compared to the group 16 Se and Te compounds.
(400 ◦ C), and mixed phases in between. Residues seen at the end of the measurements get larger in the order
As < Sb < Bi. DTA (not shown) revealed that the step of weight loss
4. Group 15 and 16 elements is accompanied by heat release (exotherm) which indicates some
decomposition. However (Et3 Si)3 As leaves practically no residue
Metal selenide and telluride thin films have been gaining contin- apparently because the decomposition products are volatile too. All
uously increasing interest. Two well-known examples are CuInSe2
solar cell absorber and Ge2 Sb2 Te5 phase change material. Phase-
change random-access memory (PCRAM) is a promising technology
for future non-volatile data storage [184–186]. Reaching high inte-
gration densities together with low power consumption in PCRAMs
requires that memory cells are scaled into dimensions of a few
nanometers only. Confinement of the phase change material into
small areas and volumes is most efficiently done by depositing the
material into tiny vias. This requires excellent conformality from
the thin film deposition method and makes ALD an attractive tech-
nique for replacing the so far dominant sputtering methods. From
the ALD chemistry point of view the common phase change mate-
rial Ge2 Sb2 Te5 (GST) was seen a major challenge because it is made
of three elements that had not been studied much earlier and were
all considered difficult to ALD.
For non-metals hydrides are often an ideal choice as they allow
clean ligand elimination by protonation. However, hydrides of
many nonmetals are highly toxic. In group 16 water of course is
without this concern, and H2 S can be used with appropriate pre- Fig. 16. TG curves measured for different alkylsilyl compounds of As, Sb, Bi, Se and
cautions because its odor threshold limit is much lower than the Te [188].
3310 T. Hatanpää et al. / Coordination Chemistry Reviews 257 (2013) 3297–3322
Fig. 17. Temperature dependencies of ALD growth rates of various materials
deposited with metal chlorides and alkylsilyl precursors of tellurium and antimony
[3,187,190].
compounds studied are sensitive to air and moisture. Compounds
with larger alkylsilyl groups are less sensitive. Most of the com-
pounds studied i.e. those with Me3 Si and Et3 Si ligands are liquids
while those with t BuMe2 Si are low melting solids.
Compounds of tellurium and selenium react efficiently with var-
ious metal halides forming the corresponding metal tellurides and
selenides. For example, Sb2 Te3 , GeTe and GST films were deposited
by ALD at remarkably low temperature of 90 ◦ C using (Et3 Si)2 Te,
SbCl3 and GeCl2 ·C4 H8 O2 as precursors, where C4 H8 O2 is a neutral
dioxane adduct ligand.
The alkylsilyl compounds of tellurium and selenium offer a
straightforward exchange reaction route to the deposition of the
metal telluride and efficient elimination of the chloride ligands of
the metal precursor, the overall reaction being:
(R 3 Si)2 Te(g) + MCl2 (g) → MTe(s) + 2R 3 SiCl(g)
In situ reaction mechanism studies with a quartz crystal
microbalance and quadrupole mass spectrometer verified the
dechlorosilylation reaction mechanism and showed that the ligand
exchange and formation of R3 SiCl as a byproduct occur stepwise
during both metal chloride and alkylsilyl tellurium pulses [189].
The favorability of this reaction is supported by the Lewis hard-
soft acid–base concept: in (R3 Si)2 Se and (R3 Si)2 Te silicon, a hard
Lewis acid, is bonded to the heavy group 16 elements which are soft
Lewis bases, thus forming an unfavorable hard-soft Lewis acid–base
pair. Upon exchange reaction with metal chlorides, silicon becomes
bonded to a harder base. Further, if the metal of the metal chloride
is a soft Lewis acid (large cation with a low charge), the other prod-
uct of the exchange reaction will form a favorable soft–soft Lewis
acid–base pair (M–Se or M–Te).
Both Sb2 Te3 and GeTe binary processes showed the self-limiting
behavior as expected in ALD, i.e. the growth rates saturated with
long enough precursor pulses. Despite the low deposition tem-
peratures the saturation level was reached with reasonably short
pulse times of only 1 s. Temperature-wise the processes showed
peculiar features compared to the ALD processes in general. The
growth of Sb2 Te3 occurred with a good rate of about 0.6 Å/cycle at
as low temperature as 60 ◦ C but above that the growth rate dropped
rapidly (Fig. 17). Also with GeTe the highest rate was achieved at
the lowest possible deposition temperature of 90 ◦ C, the limita-
tion coming from GeCl2 ·C4 H8 O2 that needs a source temperature
of 70 ◦ C [3,190]. Above 90 ◦ C the GeTe deposition rate decreased
rapidly and dropped to zero already at 150 ◦ C. Consequently the
largest concern related to these processes arises from the modest
volatility of GeCl2 ·C4 H8 O2 combined with the strong temperature
Fig. 18. Ge–Sb–Te phase diagram showing compositions reached so far with the
metal chloride–alkylsilyl tellurium/antimony based ALD processes.
dependence of the growth rate. Various alternatives have been
looked for GeCl2 ·C4 H8 O2 but no better precursor has been found
yet. Reasons for these temperature dependences are still under dis-
cussion but they seem to be related to these specific film materials
rather than this chemistry in general because zinc telluride could
be grown at a high temperature of 400 ◦ C using the same tellurium
precursor and ZnCl2 [3].
Ternary GST films were deposited by mixing the binary ALD
cycles of GeTe and Sb2 Te3 . A growth rate of about 0.30 Å/cycle was
obtained where the cycle refers to a sum of binary cycles of Ge–Te
and Sb–Te [3,191]. A common way for controlling the ternary com-
position in ALD is to vary the cycle ratio of the binary constituents.
Ideally, the film should adopt the stoichiometry corresponding to
the composition of the stable ternary compound but because GST
(1)
and related ternary materials are more alloy-like and many stoichi-
ometric compositions exist along the pseudo-binary line between
GeTe and Sb2 Te3 (Ge1 Sb2 Te4 , Ge2 Sb2 Te5 , Ge3 Sb2 Te6 , etc.) there is
no strong driving force towards a particular stoichiometry. Indeed,
in the ternary process the antimony content increased and the ger-
manium and tellurium contents decreased with increasing SbCl3
exposure times without approaching any specific composition.
Anyhow, the GST composition could still be adjusted close to the
stoichiometric Ge2 Sb2 Te5 by tuning the ratio of the binary cycles
Ge–Te and Sb–Te. On the other hand, if so desired, the composition
can be adjusted to other stoichiometries on the GeTe–Sb2 Te3 tie
line as well by just changing the binary cycle ratio.
The dechlorosilylation reaction was later extended to also ele-
mental antimony (Fig. 17) and various metal antimonides, also
those of germanium [187]. Elemental Sb films were deposited from
SbCl3 and (Et3 Si)3 Sb, while GeCl2 ·C4 H8 O2 and (Et3 Si)3 Sb deposited
a germanium–antimony alloy with a germanium rich composi-
tion of 82 at.% Ge and 18 at.% Sb. The germanium rich composition
points to a reaction mechanism more complicated than the simple
ligand exchange; most likely some antimony to germanium sub-
stitution is involved, too. Contrary to the Ge–Sb–Te system, Ge–Sb
has no stoichiometric compound and tends to elemental segrega-
tion. Anyhow, by mixing the ALD cycles of elemental Sb with those
of Ge82 Sb18 , the film composition could be tuned in between these
two extremes. Furthermore, when also GeTe and/or Sb2 Te3 ALD
cycles were added, the Ge–Sb–Te composition could be tuned over
a wide range of compositions in the ternary phase diagram (Fig. 18).
Despite the low deposition temperature, the GST films deposited
from the germanium and antimony chlorides contained reasonably
low impurity contents of about 2.4 at.% oxygen, 1.0 at.% hydrogen,
 T. Hatanpää et al. / Coordination Chemistry Reviews 257 (2013) 3297–3322 3311

0.7 at.% carbon, and 0.6 at.% chlorine as analyzed by Time-of-Flight

Energy Recoil Detection Analysis (TOF-ERDA) [3,191]. In elemen-
tal Sb films no chlorine could be detected with ERDA [187]. The
silicon residues were more difficult to analyze because the films
were on Si substrate, but the silicon content appeared to be below
1 at. %. Low levels of silicon and carbon in the GST films have
also been verified with Secondary Ion Mass Spectrometry (SIMS)
[191].
The binary Sb2 Te3 and elemental Sb films were found to grow
in polycrystalline form whereas with GeTe both amorphous and
polycrystalline films have been obtained. The ternary GST has
usually been amorphous in the as-deposited state which can be
considered as a fortunate consequence of the low deposition tem-
perature because strong crystallization during the growth could
prevent complete filling of the three-dimensional PCRAM memory
cell structures. With the amorphous GST and the GeTe films com-
plete filling of sub-100 nm holes in actual PCRAM device structures
was successfully demonstrated (Fig. 19).
Phase change properties of the ALD GST films have been studied
with high temperature X-ray diffraction and resistivity measure-
ments and compared to the sputtered GST films. In general, the
phase change properties exhibited by the ALD GST films have been
similar to their sputtered counterparts though in the ALD films
the phase change temperatures and resistivities were somewhat Fig. 19. Transmission electron microscopy image of a GeTe film filing a
31 nm × 84 nm via indicated by the arrow [190]. Reproduced with permission from
higher. The small amounts of impurities, oxygen in particular, in the J. Electrochem. Soc. 158 (2011) D694. Copyright 2011, The Electrochemical Society.
ALD GST films likely explain these differences. Laser pulse exper-
iments have verified that the ALD GST films can be repeatedly
switched between amorphous and crystalline states. fuel cells) [193–196]. Ternary and quaternary bismuth containing
While the early research on ALD of GST reviewed above was metal oxides have a wide spectrum of potential applications. These
done on films made in small research reactor with 50 mm × 50 mm include various data storage devices (DRAM, FRAM, magnetic,
substrates, later the GST ALD process was scaled up to 200 mm optical, holographic), electro-optical modulators, oxidation cata-
wafers with less than 3% 1 thickness nonuniformity [192]. lysts, gas sensors, solid oxide fuel cells, photocatalysts, lithium ion
This also allowed fabrication of integrated PCRAM devices which batteries, lasers, optical amplifier, superconductors, and oxygen
demonstrated that the memory cells with ALD GST could be conducting solid electrolytes [193]. Bismuth sulfides, selenides
switched between the low and high resistivity states up to 106 and tellurides are other materials of interest. They find use for
cycles with a very stable resistance for both states. example in thermoelectrics [197].
Unlike for example in the case of the larger alkaline earth metals
5. Bismuth strontium and barium even the simplest compounds of bismuth
, like BiCl3 , BiMe3 and Bi(Ot Bu)3 are quite volatile. This is because
Many applications have been suggested in literature for thin bismuth tends to form compounds that are monomeric or have
films containing bismuth. Binary bismuth oxide can be used in a low oligomerization degree which in turn may be explained by
sensors and solid electrolytes (ionic conductors in solid state oxide the sufficiently high electronegativity (2.02) and charge to ionic

Table 4
Compounds of bismuth used as precursors in ALD.

Precursor Other precursors Material References

BiCl3 (Et3 Si)2 Se (Et3 Si)2 Te Bi2 Se3 [3]

H2 S Bi2 Te3 [3]
Bi2 S3 [200]

Bi(Ph)3 Ti(Oi Pr)3 + H2 O Bi–Ti–O pyrochlore [201]

O3 + Ti(Oi Pr)4 + H2 O Bi4 Ti3 O12 [202]
Bi(Ph)3 and SrTa2 (OEt)10 me2 in n-butylacetate + O2 plasma SrBi2 Ta2 O9 [203]

Bi(CH2 SiMe3 )3 O3 Bi–Si–O [204]

Bi(N(SiMe3 )2 )3 Ta(OEt)5 + H2 O Bi–Ta–O [109]

Ti(OMe)4 + H2 O Bi–Ti–O pyrochlore [205]
Ti(OMe)4 + H2 O Bi4 Ti3 O12 [205]
SrTa2 (OEt)10 (dmae)2 + H2 O SrBi2 Ta2 O9 [109]

Bi(thd)3 H2 O Bi2 O3 [206,208]

Bi(OCMe2 i Pr)3 H2 O Bi2 O3 [206]

Bi(mmp)3 Bi(mmp)3 and Ti(mmp)4 in ethylcyclohexane + O3 /O2 Ti(Oi Pr)5 + H2 O Bi4 Ti3 O12 [209]
Ti(Oi Pr)4 + Si(OEt)4 + H2 O Bi–Ti–O pyrochlore [210]
Bi(mmp)3 , Ti(mmp)4 and Si(OEt)4 in ethylcyclohexane + O3 Bi–Ti–Si–O [211,212]
Bi(mmp)3 and Ti(mmp)4 in ethylcyclohexane, AlMe3 + H2 O Bi–Ti–Al–O [213]
3312 T. Hatanpää et al. / Coordination Chemistry Reviews 257 (2013) 3297–3322

radius ratio (Bi3+ , 2.91(CN = 6)) of bismuth [198,199]. So volatility

is not the main issue while trying to find suitable ALD precursors
for bismuth. The issues are more like insufficient reactivity and low
thermal stability.
ALD processes have been reported for several bismuth oxide and
chalcogenide materials. These processes are collected into Table 4.
Successful ALD has been reported for eight bismuth precursors:
BiCl3 , BiPh3 , Bi(CH2 SiMe3 )3 , Bi(N(SiMe3 )2 )3 , Bi(thd)3 , Bi(mmp)2 ,
Bi(Ot Bu)3 and Bi(OCMe2 i Pr)3 .

5.1. Bismuth chloride as precursor for ALD

BiCl3 is a volatile and thermally stable compound with a vapor

pressure of 0.1 mbar at 173 ◦ C [214]. Reported source tempera-
tures in ALD have been 140 ◦ C [3]. In the reactions with (Et3 Si)2 Se
and (Et3 Si)2 Te selenides and tellurides of bismuth are easily
formed [3]. Also Bi2 S3 can be deposited using H2 S as the sul-
fur precursor [200]. With these reactants formation of bismuth
chalcogenides is favorable and this may be partially explained by
the soft Lewis acid Bi3+ coming together with the soft Lewis base
(S2− , Se2− , Te2− ). The problem with BiCl3 is its inability to form
pure oxide films. With water, O2 and O3 the films formed are
oxychloride BiOCl or otherwise heavily contaminated by chlorine
[215].

5.2. Organometallic compounds of bismuth as precursors for ALD

Bi(Ph)3 [201–203] and Bi(CH2 SiMe3 )3 [204] are the only true
organometallic bismuth compounds that have been used for ALD.
Trialkyl and triaryl compounds of bismuth are well volatile and
they have been used largely in MOCVD. Down sides of these
compounds is their lack of reactivity against H2 O, their potential
explosion hazard and harmfulness [216]. Though Bi(Ph)3 does not
form any film with H2 O, Bi–Ti–O films with Bi/Ti ratios up to 0.6
were achieved when Bi(Ph)3 –H2 O reaction cycles were mixed with
titanium tetraisopropoxide–H2 O cycles. Further Bi incorporation
was difficult, however [201]. In addition, bismuth was incorpo-
rated into the films in a metallic form rather than as an oxide, and
post-deposition annealing was needed to oxidize bismuth. With
O3 Bi(Ph)3 forms dark non-uniform films [202]. When Bi(Ph)3 + O3
cycles were mixed with Ti(Oi Pr)4 + H2 O cycles Bi–Ti–O could be
grown [202]. In liquid injection plasma enhanced ALD of strontium
bismuth tantalate (SBT) Bi(Ph)3 has been used as a component in
the solution [203]. Simultaneous injection of two or more metal
precursors can, however, lead to composition nonuniformity while
coating deep trench structures because the precursors are com-
peting for the same chemisorption sites. Nevertheless, uniform
SBT composition over a 5-in. wafer was reported by Shin et al.
[203].
Bismuth silicates, Bix Siy Oz have been deposited from
Bi(CH2 SiMe3 )3 and O3 at temperatures between 200 and 450 ◦ C
[204]. Fig. 20 shows the structure and TGA curve measured for
Bi(CH2 SiMe3 )3 . TG curve for Bi(i Pr)3 is included for volatility com-
parison. In the Bi(CH2 SiMe3 )3 –O3 process Bi(CH2 SiMe3 )3 acted as
a precursor for both bismuth and silicon. Constant growth rate
of 0.4 Å/cycle independent of the Bi(CH2 SiMe3 )3 precursor pulse
time above 1 s was observed at 250–350 ◦ C. Films deposited above
350 ◦ C showed a clear thickness profile indicating decomposition
of the precursor. The Si/Bi ratio increased with the increasing
deposition temperature but in the films deposited at 250–350 ◦ C
the ratio was around 2. The as-deposited films were amorphous
but annealing either in N2 or O2 atmosphere resulted in crystalline
films showing the presence of orthorhombic Bi2 SiO5 phase and
some other bismuth silicates.
Fig. 20. Above: Molecular structure of Bi(CH2 SiMe3 )3 . Below: TG curves of Bi(i Pr)3
and Bi(CH2 SiMe3 )3 [204].
5.3. Tris(Bis(Trimethylsilyl)amido)Bismuth(III) as a precursor for
ALD
Even the simplest alkylamides of bismuth like Bi(NMe2 )3 are
known to be monomeric and quite volatile [217], and they have
been mentioned as possible MOCVD precursors though actual
usage has not been reported. Down sides of these compounds
considering ALD usage are their light sensitivity, extremely high
sensitivity to air and moisture, and thermal instability. Compared
to simple alkylamides the silylamide Bi(N(SiMe3 )2 )3 is more stable
and less sensitive [109]. TGA under normal pressure N2 atmosphere
shows a single step weight loss of 98% at 220–270 ◦ C (Fig. 21). This
result suggests that Bi(N(SiMe3 )2 )3 is stable even up to 270 ◦ C, but
ALD growth experiments implied that decomposition takes place
already at temperatures exceeding 200 ◦ C. The compound melts at
133–137 ◦ C and was a solid at 120 ◦ C ALD source temperature used.
ALD Growth of BiOx was achieved at very narrow temperature win-
dow between 190 and 200 ◦ C using Bi(N(SiMe3 )2 )3 and H2 O as the
precursors. Uniform amorphous BiOx thin films could be deposited
with growth rates between 0.08 and 0.23 Å/cycle, but the repro-
ducibility of the process was poor [109]. The irreproducibility in
the binary oxide growth was thought to be due to partial reduction
of bismuth to metallic form, leading to termination of the growth
[205]. Other peculiarities in the BiOx growth were also observed.
FESEM revealed that the grown amorphous BiOx films were granu-
lar while amorphous films are usually smooth and featureless. The
 T. Hatanpää et al. / Coordination Chemistry Reviews 257 (2013) 3297–3322
Fig. 21. Above: Crystal structure of Bi(N(SiMe3 )2 )3 . Below: TG curve of
Bi(N(SiMe3 )2 )3 (N2 , 1 atm, 10 ◦ C/min, ∼10 mg sample) [109].
granular morphology was thought to originate from a reduction of
bismuth to an elemental form at some point of the growth, followed
by its reoxidation during the further deposition cycles as there was
no metallic bismuth in the films [205].
Deposition of tantalum and titanium containing multi-
component films was found more reproducible than BiOx
deposition. It is likely that mixing the BiOx growth cycles with the
other metal oxide cycles stabilizes the growth. Multicomponent
Bi–Ta–O, Sr–Bi–Ta–O [109] and Bi4 Ti3 O12 [205] films were
made by mixing Bi(N(SiMe3 )2 )3 –H2 O cycles with Ta(OEt)5 –H2 O,
SrTa2 (OEt)10 (dmae)2 –H2 O and Ti(OMe)4 –H2 O cycles. The film
growth was similarly found to be limited to 190–200 ◦ C and below
by the thermal stability of Bi(N(SiMe3 )2 )3 . In the case of all the mul-
ticomponent oxides the metal component ratios could be varied by
varying the binary oxide cycle ratios.
When Bi–Ta–O was deposited at 190 ◦ C using a fixed BiOx /Ta2 O5
cycle ratio of 2:1 Bi–Ta–O the growth rate was 0.33 Å/cycle and
the Bi/Ta ratio was around 1.1. Amorphous Sr–Bi–Ta–O (SBT) films
were deposited by mixing two Bi(N(SiMe3 )2 )3 –H2 O cycles with one
SrTa2 (OEt)10 (dmae)2 –H2 O cycle. The films deposited were found
strontium deficient with a stoichiometry of Sr0.8 Bi2.1 Ta2 Ox though
the Sr/Ta ratio in the precursor was fixed to 1:2. The desired ferro-
electric layered perovskite, i.e. the so-called Aurivillius phase SBT
was realized after careful annealing treatments but still there was
always some pyrochlore phase present in the films. Permittivity of
3313
Fig. 22. Sawyer-Tower Q–V loop of a Pt/SBT/Pt capacitor structure [70].
70 and remanent polarization of 0.75 ␮C/cm2 were measured for
190 nm SBT film (Fig. 22) [70].
Mixing Bi(N(SiMe3 )2 )3 –H2 O cycles with Ti(OMe)4 –H2 O cycles
in 1:1 ratio resulted in smooth amorphous films with a Bi/Ti ratio of
0.33. 7:1 cycle ratio was needed for obtaining phase-pure Bi4 Ti3 O12
films with sufficient Bi content. Crystallization of the Bi–Ti–O films
was carried out at 500–750 ◦ C. Ferroelectric films with remanent
polarizations up to 0.5 ␮C/cm2 (51 nm film) were prepared on
Pt/SiO2 /Si-substrates by annealing first at 500 ◦ C and then at 600 ◦ C
[70].
Main limitations of the Bi(N(SiMe3 )2 )3 precursor are its low
thermal stability and the high evaporation temperature needed
that together limit the growth temperature to very narrow range
of 190–200 ◦ C. The tendency of the precursor to deposit binary bis-
muth oxide unreliably is a further limitation. In addition, it is also
likely that with O3 there would be silicon incorporation in the films.
5.4. Bismuth compounds with oxygen based ligands as precursors
for ALD
Several bismuth compounds with oxygen based ligands are
known and their thermal properties have been studied. Volatile
compounds can be found in all the common compound groups i.e.
alkoxides, ␤-diketonates and carboxylates.
5.4.1. ˇ-Diketonates of bismuth
Several ␤-diketonates of bismuth are known [218]. They are
volatile, sufficiently thermally stable compounds and they react
with H2 O. In ALD only Bi(thd)3 has been used [206–208]. Bi(thd)3
forms loose dimers in the solid state (Fig. 23) and is most likely
monomeric in the gas phase. Bi(thd)3 melts at 130–134 ◦ C and TGA
shows 97% weight loss in a single step at 160–300 ◦ C indicating
evaporation (Fig. 24). Bi2 O3 was deposited from Bi(thd)3 and H2 O
at temperatures between 200 and 350 ◦ C. The ALD temperature
window was found at 270–300 ◦ C but the growth rate was low,
0.1 Å/cycle, and believed to be due to the large steric hindrance of
the ligands.
5.4.2. Bismuth alkoxides
Bismuth alkoxides form an interesting group of bismuth pre-
cursors. The simplest alkoxides Bi(OMe)3 , Bi(OEt)3 , Bi(Oi Pr)3
have very poor volatility but even the smallest tertiary alkoxide
Bi(Ot Bu)3 may be sublimed cleanly already at 80–100 ◦ C/0.05 mbar
[206,219,220]. It seems that in general bismuth alkoxides with ter-
tiary alkoxy ligands have good volatility while those with primary
or secondary alkoxy ligands do not. There are several examples
which show that the structures of bismuth alkoxides with pri-
mary or secondary alkoxy ligands are oligomeric while the ones
3314 T. Hatanpää et al. / Coordination Chemistry Reviews 257 (2013) 3297–3322
Fig. 23. Molecular structure of Bi(thd)3 . Loose dimers are formed in solid state.
Fig. 24. TG curves of different bismuth alkoxides, ␤-diketonate Bi(thd)3 and carbox-
ylates Bi(O2 Ct Bu)3 and Bi(O2 CMe)3 [206]. Reproduced by permission of The Royal
Society of Chemistry.
with tertiary alkoxy ligands are monomeric [219,221]. Structures
of Bi(Ot Bu)3 and Bi(Oi Pr3 )3 are shown in Fig. 25. Among the bis-
muth alkoxides with tertiary alkoxy ligands the volatility seems to
decrease with increasing molecular weight i.e. Bi(Ot Bu)3 is the most
volatile as can be seen from TG curves shown in Fig. 24. Thermal
stability of Bi(Ot Bu)3 however is not good and it was found that
a compound with a bit larger alkoxy ligand–OCMe2 i Pr seems to
be more stable. Using even larger tertiary alkoxy ligands seems to
lower the thermal stability. Bismuth alkoxides are in general well
reactive with water though the reaction is not vigorous.
Bi(Ot Bu) has been only tested in a preliminary manner for ALD
of Bi2 O3 using H2 O as the oxygen precursor [206]. Bi2 O3 film grew
but the precursor, solid at the evaporation temperature of 70 ◦ C
(mp. 139 ◦ C), seemed to suffer from ageing making repeatable ALD
impossible.
Bi(OCMe2 i Pr)3 is more stable alkoxide and was studied in more
detail [206]. Bi(OCMe2 i Pr)3 has the advantage of being a liquid (mp.
40 ◦ C) at the temperature used for its evaporation (85 ◦ C). At 150 ◦ C
the Bi(OCMe2 i Pr)3 –H2 O process was found to produce Bi2 O3 with
a growth rate of 0.38 Å/cycle. ALD type growth was verified fully
at this temperature but it was also confirmed that no significant
decomposition took place even at temperatures of 200–250 ◦ C. At
240 ◦ C the growth rate was found to be 0.30 Å/cycle [200,222]. Films
grown at 150 ◦ C were amorphous as-deposited while at growth
Fig. 25. Molcular structures of Bi(Ot Bu)3 (above) and Bi(OCi Pr3 )3 (hydrogen atoms
omitted for clarity) [206].
temperatures above 200 ◦ C a thus far unidentified crystalline bis-
muth oxide phase was observed. TOF-ERDA results revealed that
the films were oxygen rich, probably due to OH residues, and had
otherwise very low impurity levels.
Bi(OCMe2 i Pr)3 has also been studied in ALD of Bi4 Ti3 O12 and
SrBi2 Ta2 O9 at 240 ◦ C [200,222]. For Bi4 Ti3 O12 the other precursors
were Ti(OMe)4 and H2 O. Mixing Bi(OCMe2 i Pr)3 –H2 O cycles with
Ti(OMe)4 –H2 O cycles in a 3:1 ratio gave a Bi/Ti ratio of 1.47 in the
film. Bi4 Ti3 O12 , an orthorhombic ferroelectric phase was observed
after annealing the films in air at 700 ◦ C. For SrBi2 Ta2 O9 the other
precursors used were Ta(OEt)5 , Sr(i PrC5 H2 )2 or Sr(t Bu3 C5 H2 )2 , and
H2 O.
Bi(mmp)3 i.e. Bi(OCMe2 CH2 OMe)3 is an alkoxide with a tertiary
donor functionalized ligand. This compound has a very good volatil-
ity and can be sublimed at 60 ◦ C/0.01 mbar. It has been used to
deposit Bix Tiy Oz , Bix Tiy Siz Ow and Bix Tiy Alz Ow (Table 4) [209–213].
In three studies Bi(mmp)3 was delivered by liquid injection as a part
of a solvent mixture [209,212,213]. In two studies Bi(mmp)3 –H2 O
cycles were combined with Ti(Oi Pr)4 –H2 O and Si(OEt)4 –H2 O cycles
and the ALD type of growth of Bi–Ti–O and Bi–Ti–Si–O were
reported at 225 ◦ C [30,211]. Our own studies on the Bi(mmp)3 –H2 O
process revealed that the precursor was decomposing quite rapidly
at 250 ◦ C [200]. Bi(mmp)3 was also seen to suffer from ageing in the
heated source.
 T. Hatanpää et al. / Coordination Chemistry Reviews 257 (2013) 3297–3322 3315

5.4.3. Bismuth carboxylates

Carboxylates form another group of bismuth compounds that
may be potential ALD precursors. Bismuth formate is completely
unvolatile but acetate and other primary and secondary carboxyl-
ates may be sublimed at 200–230 ◦ C under vacuum with 70–80%
yields [223]. Bismuth pivalate, Bi(O2 Ct Bu)3 , which has tetrameric
structure [224], can be sublimed already at 160 ◦ C/0.05 mbar and is
stable up to 400 ◦ C [206,223]. TG measured under normal pressure
N2 atmosphere also shows almost complete evaporation before
310 ◦ C (Fig. 24). Clear advantages of Bi(O2 Ct Bu)3 are high thermal
stability, easy handling and synthesis which does not require any
exclusion of air and moisture. Disadvantage is the lack of reactiv-
ity against H2 O and O2 . Bi(O2 Ct Bu)3 has been tested with H2 O for
ALD only preliminarily and it was found that at 250 ◦ C there was no
growth and at 300 ◦ C the growth rate was 0.06 Å/cycle. With more
powerful oxidizing reagents like O3 or oxygen plasma it may be
possible to deposit bismuth oxide more efficiently.

6. Pt group metals

Thin films of noble metals and their oxides find use in a wide
variety of applications from catalysis to microelectronics. In inte-
grated circuits there main use is as electrode materials in MOSFETs
and various memory capacitors. The main benefits of noble metals
are high work function and resistance against oxidation, and even
if oxidized under oxygen plasma or ozone, the resulting noble
metal oxide layers are still conducting. On the other hand, noble
metal oxides are sometimes preferred as the bottom electrodes
because their structural compatibility with high-k oxides promotes
the crystallization of the latter.
ALD of noble metals was done for the first time in 2003 when Ru
was deposited from RuCp2 and O2 [225,226]. In this case the success
can be attributed more to the reactant rather than the metal pre-
cursor. Before that molecular oxygen had been considered mostly
unreactive in ALD as only in a few special cases it could have been
used for ALD of oxides. Therefore it was surprising to observe O2
serving as an efficient reactant for ALD of noble metals where reduc-
ing agent in the first place was looked for. The high reactivity in the
noble metal ALD process was concluded to be due to the activation
of O2 by the noble metal film itself via dissociative adsorption into
atomic oxygen. Indeed, in situ reaction mechanism studies revealed
that the RuCp2 –O2 ALD Ru process involved combustion reactions
producing CO2 and H2 O as the main byproducts [225,227]. Sub-
stantial amount of these were released already during the RuCp2
pulse which was interpreted in terms of atomic oxygen remaining
adsorbed on, and to some extent also in, the Ru film surface after
the O2 pulse. Later a similar process was demonstrated using a
␤-diketonate Ru(thd)3 [228], thereby showing that the metal pre-
cursor does not need to be an organometallic compound, and the O2
based noble metal ALD chemistry was expanded to Rh [229–231],
Pd [231,232], Os [233], Ir [231,234–236], Pt [231,232,234,235].
The O2 based ALD metal processes suffer, however, from poor
nucleation. This is thought to be due to a lack of catalytic activation
of O2 before the first nuclei of the noble metal form, a mecha-
nism which is still to be explained. Also the growth temperatures
needed with O2 are typically 225 ◦ C and above. Therefore ozone
as a more efficient oxidizing agent was tested in place of O2 and
was found to enable film deposition at much lower temperatures
than O2 [237–240]. Typically films deposited below about 200 ◦ C
were noble metal oxides and those deposited above 200 ◦ C were
metallic even when ozone was used. On the other hand, when H2
was added in the pulsing sequence (metal-precursor–O3 –H2 ) noble
metals could be deposited at as low temperatures as 165 ◦ C [238].
Taking Ir and IrO2 as an example, the first process examined
was Ir(acac)3 –O2 that deposited metallic Ir at 225 ◦ C and above
Fig. 26. Above: Molecular structure of (MeC5 H4 )Ir(CHD). Below: TG and SDTA
curves of the compound [236]. Reproduced by permission of The Royal Society of
Chemistry.
[236]. When O2 was replaced with ozone, the Ir(acac)3 –O3 pro-
cess deposited IrO2 at 165–200 ◦ C and metallic Ir above 200 ◦ C.
The low temperature limit of 165 ◦ C was in this case set by the
low volatility of Ir(acac)3 that requires a source temperature of
155 ◦ C [239]. In other words, with the introduction of O3 –H2 [238]
in place of O2 , the metal precursor Ir(acac)3 became the limiting
factor for the low temperature deposition of Ir and created a
need for new iridium precursor. To fill this gap, (MeCp)Ir(CHD)
(MeCp = methylcyclopentadienyl, CHD = cyclohexadiene) was syn-
thesized and tested with both O2 and O3 [236,241]. (MeCp)Ir(CHD)
has a mp of 36–39 ◦ C and could be delivered from a source tem-
perature of 45–50 ◦ C. Structure and TG/SDTA curves are shown
in Fig. 26. The (MeCp)Ir(CHD)–O2 process was effective only at
225 ◦ C and above depositing metallic Ir and was thus similar to the
Ir(acac)3 –O2 process. By contrast, the (MeCp)Ir(CHD)–O3 process
deposited iridium oxide films from as low as 100 ◦ C up to 180 ◦ C
while at 200 ◦ C metallic iridium was obtained. Upon adding hydro-
gen the (MeCp)Ir(CHD)–O3 –H2 process deposited metallic iridium
films down to 120 ◦ C.
7. Silver
Silver has the lowest resistivity of all known elements,
1.59 ␮ cm, and is highly reflective and antibacterial material.
Thus silver is used in electrical conductors, highly reflective mir-
rors decorative coatings and antimicrobial coatings [242]. In future
silver could be used in microelectronics interconnects [243]. Com-
pared to many other conducting elements like gold, silver and its
3316 T. Hatanpää et al. / Coordination Chemistry Reviews 257 (2013) 3297–3322

compounds are cheap. Recently, silver nanostructures have

achieved much attention as substrate materials for surface
enhanced Raman scattering [244].
Silver is a group 11 element and resides between Cu and Au. The
most common oxidation state of silver is +I. Pauling’s electroneg-
ativity of silver is 1.9 [198] which cause less polar bonds to form
with ligands if compared for example alkaline earth metals. Ionic
radius of Ag+ is 0.67 Å (CN = 2) [199] and the charge to radius ratio
1.49 which means that AgL compounds should be keen to increase
their coordination number through oligomerization or adduct for-
mation. Ag+ is a soft Lewis acid and thus forms stronger bond with
soft Lewis bases like phosphorus and sulfur.
Considering ALD of silver films the main issues are finding a
silver precursor with sufficient thermal stability and choosing a
suitable co-precursor which converts the silver precursor to a sil-
ver film. Most of the known silver compounds which show volatility
are thermally quite unstable. In the case of the platinum group
metals (Ru, Os, Rh, Ir, Pd, Pt) the usage of O2 , O3 and O3 + H2 as
co-precursors has been found to result in good quality metal films
from many kinds of noble metal precursors (see above). In the case
of silver this approach apparently has not been found effective and
to date the ALD of silver films has relied on using a reducing agent
[245–247].
While looking for silver precursors for CVD the main objec-
tive has been to make a volatile compound which decomposes at
relatively low temperature in the CVD apparatus [248]. This is in
contrast with the demands set for good ALD precursor which should Fig. 27. Molecular structure of [Ag(i PrNCMeNi Pr)]2 (PEt3 ) [259].
not show any decomposition. The most common silver precursors
used for CVD are ␤-diketonates and carboxylates with and with- PEt3 was added in 1:1 proportion. Bi(Piv)3 (Ag5) is polymeric in the
out adduct forming ligands [248]. Many of the compounds with no solid state [260] and Ag3 and Ag4 are also believed to be polymeric.
adduct forming ligands are oligomeric or polymeric with low or no Ag6 forms a trimeric structure shown in Fig. 28 [245]. Ag7 with the
volatility. In several studies on CVD precursors with oxygen based larger phosphine ligand PBu3 forms a dimer [261]. Ag8 is believed
ligands it has been noticed that the volatility of the complexes is to be polymeric and Ag9 is a monomeric [262]. In Ag10 there is
improved when ligands with appropriate bulkiness and/or fluori- a weak interaction between Ag atoms of two Ag(thd)(PEt3 ) units
nation are used. It has also been noticed that adduct forming ligands i.e. the compound is dimeric (Fig. 29) [246]. Ag(fod)(PEt3 ) (Ag11)
and their type have crucial effect on the thermal stability and shows a dimeric structure where the ␤-diketonato ligands which
volatility of the complexes. Electronic properties i.e. the ␲-acceptor are chelated to one Ag atom also share one oxygen atom with the
strength of the adduct forming ligands seem to be especially impor- second Ag atom(Fig. 30) [246]. The bridging O atom is on the side
tant. Neutral ligands introduced silver complexes include alkene of the C3 F7 -chain of the fod ligand. Ag atoms are not interacting
[249], alkyne [250], methylisocyanide [251], polyamines [252], but there is an interaction between a F atom and Ag (Ag–F distance
polyethers [253,254] and phosphines [248]. Phosphines seem to 3.111 Å).
form the strongest bonds with silver. The Ag–O bond stability of To study the volatility and thermal stability of the compounds
compounds with tertiary phosphines as adduct forming ligands TGA/SDTA measurements were done (Fig. 31). All the prepared
increases in order: PMe3 < PEt3 < PPh3 , following the ␲-acceptor compounds except Ag(fod)(PEt3 ) (Ag11) left residues which were
strength of the ligands. However, PPh3 is not a good ligand consid-
ering the volatility.
ALD of silver is quite scarce and there seem to be only
three different processes reported [245–247]. Chalker et al. used
Ag(hfac)(COD) and propanol and the resulting deposits were sil-
ver nanoparticles rather than thin films [247]. In our own work
we employed plasma activated hydrogen to deposit silver from
Ag(Piv)(PEt3 ) and Ag(fod)(PEt3 ) [245,246].
While looking for the most promising precursors for ALD a
set of silver compounds was synthesized and studied. The com-
pounds studied were amidinates, carboxylates and ␤-diketonates:
Ag(i PrNCMeCCi Pr) (Ag1), [Ag(iPrNCMeCNiPr)]2 (PEt3 ) (Ag2),
Ag(O2 CMe) (Ag3), Ag(O2 CCF3 ) (Ag4), Ag(Piv) (Ag5), Ag(Piv)(PEt3 )
(Ag6), Ag(Piv)(PBu3 ) (Ag7), Ag(fod) (Ag8), Ag(hfac)(PMe3 ) (Ag9),
Ag(thd)(PEt3 ) (Ag10), Ag(fod)(PEt3 )(Ag11). Structures of com-
pounds Ag2, Ag6, Ag10 and Ag11 were solved while the structures
of Ag1, Ag5, Ag7 and Ag9 were already known. Amidinate Ag1
forms dimers and trimers in the same cystal structure [258].
Different N atoms in the ligand bond to different Ag atoms. By
adding PEt3 to this compound it was hoped that a monomer would
form. However this did not happen and instead a dimer with one
PEt3 bonded to one Ag atom (Ag2) was seen (Fig. 27) [259], though Fig. 28. Molecular structure of [Ag(Piv)(PEt3 )]3 [245]. Trimeric structure.
 T. Hatanpää et al. / Coordination Chemistry Reviews 257 (2013) 3297–3322 3317

Fig. 29. Molecular structure of Ag(thd)(PEt3 ) [246]. Dimeric structure.

Fig. 30. Molecular structure of Ag(fod)(PEt3 ) [246]. Dimeric structure.

larger or approximately equal with the theoretical amount of

Fig. 31. TG curves of different silver compounds prepared.
silver in the compounds i.e. the compounds decomposed. In con-
trast, Ag(fod)(PEt3 ) left only a 6% residue while the Ag content
is 22.7%, which proves that most of the compound evaporated.
All the compounds studied except Ag(fod)(PEt3 ), which showed
an endotherm due to evaporation, also showed heat release dur-
ing the TG/SDTA measurements indicating decomposition. TGA
lets us to suggest that Ag(fod)(PEt3 ) could be thermally stable
at least up to 230 ◦ C, but ALD experiments showed that already
at temperatures exceeding 140 ◦ C there was thermal decom-
position [246]. Considering the temperature where the weight
change takes place in TGA being an indication of thermal sta-
bility of the compounds in the condensed state (solid, liquid),
the thermal stability increases in order: [Ag(i PrNCMeNi Pr)]2 (PEt3 )
(Ag2) < Ag(i PrNCMeNi Pr) (Ag1) < Ag(fod) (Ag8) < Ag(hfac)(PMe3 )
(Ag9) ∼ Ag(thd)(PEt3 ) (Ag10) < Ag(Piv)(PEt3 ) (Ag6) ∼ Ag(Piv)(PBu3 )
(Ag7) < Ag(O2 CMe) (Ag3) ∼ Ag(Piv) (Ag5) < Ag(O2 CCF3 ) (Ag4), the
most stable being the unadducted carboxylates. For Ag(fod)(PEt3 )
(Ag11) it is more complicated to evaluate the temperature of
decomposition as the compound evaporates but roughly it could
3318 T. Hatanpää et al. / Coordination Chemistry Reviews 257 (2013) 3297–3322
Fig. 32. SEM pictures of Ag films deposited using the Ag(Piv)(PEt3 )–H radicals process [245]. Reproduced with a permission from Chem. Vap. Dep. 13 (2007) 408. Copyright
2007, John Wiley and Sons.
be similar with that of Ag(Piv)(PEt3 ). Clearly, for all the other sil-
ver compounds studied except Ag(fod)(PEt3 ) the temperature of
efficient evaporation at 1 atm is higher than the temperature of
decomposition. Indeed, the volatility of the carboxylates is so low
that sublimation even under vacuum requires temperatures so
high that partial decomposition, indicated by the low sublimation
yields, takes place [255]. It seems obvious that in Ag(fod)(PEt3 )
the volatility and thermal stability are in optimal balance. In
addition to Ag(fod)(PEt3 ) literature reports some other silver com-
pounds which show evaporation before decomposition in TGA.
These include Ag(thd)(Pn Bu3 ) [256], Ag(fod)(PMe3 ), Ag(fod)(PEt3 )
[257] and Ag(hfac)(C≡NMe) [251].
It does not seem to be possible to make any straight con-
clusions concerning the thermal stabilities of the compounds on
Fig. 33. (a) AFM image of a 17 nm thick Ag film deposited at 120 ◦ C. (b) SEM image
of the same film [246]. Reproduced with permission from Chem. Mater. 23 (2011)
2901. Copyright 2011 American Chemical Society.
basis of the crystal structures. Concerning the volatility, poly-
meric compounds are less volatile than the monomeric or dimeric
compounds.
In an early work Ag(Piv)(PEt3 ) was employed as the silver
precursor and hydrogen radicals produced with remote plasma
(REALD) were used as the reducing agent [245]. In addition
Ag(Piv)(PBu3 ) was tested. It was found that the Ag(Piv)(PEt3 ) pre-
cursor starts to decompose at temperatures above 160 ◦ C. As the
precursor needed to be heated to 125 ◦ C to volatilize it, the ALD
window was limited to 140–160 ◦ C. It was confirmed that the
usage of molecular H2 did not yield any films while H radicals
did work. Growth of Ag films saturated with 3 s Ag(Piv)(PEt3 ) and
7 s hydrogen radical pulses and the growth rate was 1.2 Å/cycle.
The films grew conformally as can be seen from the SEM picture
(Fig. 32). The films were quite rough but appeared mirror-like.
Impurity levels of the films were quite high on P (4.0 at.%), O
(10 at.%), H (5.0 at.%) and Si (4.0 at.%). Carbon content was only
1.0 at.%. Resistivity of a 40 nm film was measured to be 6 ␮ cm.
With Ag(Piv)(PBu3 ) films grew slowly, the resistivities of the films
were high and their appearance was dark. The worse results were
assumed to be possibly due to slower reaction kinetics or the PBu3
ligands leaving more impurities in the films. Later on upscaling
the Ag(Piv)(PEt3 )–H plasma process was tried on 200 mm Si wafers
but no uniform films could be deposited over the whole substrate.
To overcome this limitation another precursor Ag(fod)(PEt3 ) was
introduced.
Ag(fod)(PEt3 ) was used with plasma-activated hydrogen
(PEALD) [246]. Again, mirror-like continuous films were deposited
on silicon and glass substrates with a diameter of 200 mm. Films
thinner than 10 nm were non-continuous as the growth was found
to start with a formation of nanoclusters. The rms-roughness
of a 17 nm thick film was 4.8 nm and a 50 nm film had rough-
ness of 5.4 nm (Fig. 33). ALD-window for the process was found
at 120–140 ◦ C. At 120 ◦ C the growth rate was 0.3 Å/cycle and at
140 ◦ C, where some signs of decomposition were already seen,
0.38 Å/cycle. The observed growth rate is much lower compared
to that observed for the Ag(Piv)(PEt3 )–H radicals process and this
may be due to the larger fod ligand. The deposited films were
polycrystalline and the resistivity of a 22 nm film was 6–8 ␮ cm.
Elemental contents of a 17 nm film deposited at 120 ◦ C were Ag
(85 at.%), H (3 at.%), C (3 at.%), O (0.9 at.%), P (0.9 at.%), F (0.5 at.%)
and N (0.7 at.%) as measured with TOF-ERDA. It is notable that the F
contents of the films were low though there was even a Ag–F inter-
action in the solid state structure of the precursor. Also the films
contained considerably less impurities than the films deposited
with the Ag(Piv)(PEt3 )–H radicals process. These differences may,
however, be partly affected by the reactor configurations too. Any-
how, a clear advantage of Ag(fod)(PEt3 ) over Ag(Piv)(PEt3 ), as tested
in the same reactor, is the ability to deposit uniform films over large
area substrates.
 T. Hatanpää et al. / Coordination Chemistry Reviews 257 (2013) 3297–3322
8. Summary and conclusions
Precursors form the basis upon which the successful exploita-
tion of ALD is built on. Each thin film material of an interest can
be deposited with all the advantageous features of ALD only after
finding proper precursors. While ALD precursor development has
mostly been focused on metal precursors, advances in non-metal
precursors and co-reactants have brought the ALD technology for-
ward as well. Also, innovative combinations of the precursors have
opened new avenues in the ALD chemistry. In University of Helsinki
the ALD precursor chemistry research has been a balanced combi-
nation of basic and applied research, i.e. it has been driven by both
scientific curiosity and needs of industry.
In 1990s ␤-diketonates of alkaline earth metals were intensively
studied as precursors for ALD of sulfide films which act as phos-
phors in thin film electroluminescent displays. The studies were
especially aiming to blue light emitting films. As alternatives to
the ␤-diketonates, alkaline earth cyclopentadienyls were devel-
oped and tested. While the cyclopentadienyls brought only minor
improvements to the sulfide ALD, they turned highly valuable in
ALD of alkaline earth oxides containing films, in particular SrTiO3 ,
BaTiO3 and (Ba,Sr)TiO3 , that became of interest at the end of 1990s
as possible high permittivity dielectric materials for DRAM capac-
itors but could not deposit from the ␤-diketonates with water.
The best cyclopentadienyl compounds for this purpose were those
with sufficiently bulky cyclopentadienyl ligands i.e. Ca(i Pr3 C5 H2 )2 ,
Sr(t Bu3 C5 H2 )2 and Ba(t Bu3 c5 H2 )2 . To date cyclopentadienyl com-
pounds are the state-of-the-art alkaline earth metal precursors for
ALD.
ALD of group 4 oxide films has been studied for over 20 years
at the University of Helsinki. Metal chloride–H2 O processes were
studied in detail and also processes where metal chloride reacts
with metal alkoxide to form binary or mixed metal oxide were
invented. While the simple alkoxides are relatively good precur-
sors for titanium, those of zirconium and hafnium suffer from poor
thermal stability donor functionalized alkoxides of Zr and Hf were
found thermally more stable but suffered from low reactivity. Alky-
lamides form an important precursor group for group 4 metals,
especially for Zr and Hf. They are very reactive with water but
the thermal stability is limited. Films grown from the alkylamides
show in addition advantageous phase outcome where the high per-
mittivity tetragonal and cubic phases are dominating. Yet another
group of group 4 precursors studied at University of Helsinki has
been cyclopentadienyl compounds. The bis-cyclopentadienyl com-
pounds react rapidly with both water and ozone and the resulting
oxide materials are very pure. The thermal stability of the bis-Cp
compounds is higher than that of alkoxides and alkylamides and
deposition temperatures > 300 ◦ C are achievable for ZrO2 and HfO2 .
The Cp-precursors offer good thermal stability but modest growth
rate and tendency to form films with a mixture of oxide phases.
In heteroleptic complexes (CpR)Zr(NMe2 )3 (R = H, Me or Et) the
benefits of the both precursor types can be combined.
Our studies on group 15 and 16 elements were initiated by
a need to deposit germanium antimony telluride films for phase
change memory applications. The key was to find suitable tel-
lurium precursor and among the many candidates studied the
alkylsilyl compounds were most promising. They react efficiently
with metal chlorides like GeCl2 ·dioxane and SbCl3 forming the
desired tellurides. Immediately it was also realized that the chem-
istry may be expanded to other group 16 elements and also group
15 elements.
Studies on bismuth precursors were motivated by the bis-
muth containing ternary oxides. Different bismuth compounds
were synthesized and the most suitable for the oxide processes
has so far been a bismuth alkoxide Bi(OCMe2 i Pr)3 with tertiary
alkoxy ligands. With this low melting, volatile and thermally stable
3319
compound and H2 O good quality films could be deposited reliably
in a wide temperature range.
Noble metal film deposition by ALD has been a subject at Uni-
versity of Helsinki for over 10 years. The first reported ALD process
for noble metals was a ruthenium process using RuCp2 and O2 as
the precursors. Afterwards also all the other platinum group metals
(Rh, Pd, Os, Ir, Pt) were deposited using the O2 based chemistry
and various kinds of noble metal precursors. By changing O2 to
a more efficient oxidizing agent O3 oxide films of these metals
could be deposited at temperatures below 200 ◦ C while metals were
obtained above 200 ◦ C. Adding H2 to the pulsing sequence (metal
precursor–O3 –H2 ) metal films could be deposited at low temper-
atures with the evaporation temperature of the metal precursor
often being the limit. For example, Ir was deposited at 120 ◦ C using
a highly volatile Ir precursor (MeCp)Ir(CHD).
ALD of silver has remained quite scarce so far. We have stud-
ied a set of silver precursors and found two promising compounds
for ALD of silver films both containing anionic bidentate oxygen
donor ligand and a neutral phosphine adduct ligand. The silver film
ALD requires the use of hydrogen radicals or plasma as a reducing
reactant. Uniform silver thin films have been deposited on 200 mm
wafers.
The role of precursor chemistry has been and will also in the
future be crucial in developing new ALD processes and thereby
bringing the whole ALD technology forward. In the future the chal-
lenges for ALD precursor chemistry are still to find precursors
and precursor combinations for making new materials and mate-
rials whose deposition need improvement. New materials could
be for example halides other than fluorides, borides and sulfates.
Processes needing serious improvements are many and as an exam-
ple one could mention electropositive metals (Al, Ti), nitrides and
ternary compounds. There will always be also need to fine tune the
properties of the precursor compounds to fulfill the requirements
of film deposition for different applications. For designing and syn-
thesizing metal precursors there is a set of known ligands available.
A recent trend has been to combine different ligands in heteroleptic
compounds in order to combine the best properties of each ligand
type. This approach has already been successful for example in the
case of group 4 metals and will most likely be explored for also other
metals in the future. On the other hand, while looking for new pre-
cursors for ALD, it should be kept in mind that besides completely
new exotic compounds there is a large variety of known compounds
synthesized earlier for some other purpose or just for curiosity that
could be possible precursors for ALD too; they just have not been
found for the purpose yet. Also it should be remembered that the
non-metal precursors, reducing agents and other co-reactants may
be as crucial for the success in ALD as the metal precursors.
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