Europium “Second Generation” Precursors for Metal-Organic Chemical Vapor Deposition: Characterization and Optical Spectroscopy

Malandrino, Graziella; Bettinelli, Marco; Speghini, Adolfo; Fragalá, Ignazio L.

doi:10.1002/1099-0682(200104)2001:4<1039::aid-ejic1039>3.0.co;2-2

Cited by 29 publications

(10 citation statements)

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“…The Fragalà group 369 also prepared Ce(hfac) 3 ·diglyme, Ce(hfac) 3 ·diethyldiglyme and Ce(hfac) 3 ·dibutyldiglyme, and found these complexes are ideal for CeO 2 film depositions due to their high volatility and high thermal stability with low residue. Malandrino et al 370 synthesized novel complex precursors Eu(hfac) 3 ·glyme (glyme = mono- or di-) and found that both complexes are thermally stable and could be evaporated with < 4% residue. Another study by this group 371 suggested that La(hfac) 3 ·diglyme could be evaporated from the melt up to 130 °C without side decomposition processes.…”

Section: Other Applicationsmentioning

confidence: 99%

Glymes as versatile solvents for chemical reactions and processes: from the laboratory to industry

2014

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Glymes, also known as glycol diethers, are saturated non-cyclic polyethers containing no other functional groups. Most glymes are usually less volatile and less toxic than common laboratory organic solvents; in this context, they are more environmentally benign solvents. However, it is also important to point out that some glymes could cause long-term reproductive and developmental damages despite their low acute toxicities. Glymes have both hydrophilic and hydrophobic characters that common organic solvents are lack of. In addition, they are usually thermally and chemically stable, and can even form complexes with ions. Therefore, glymes are found in a broad range of laboratory applications including organic synthesis, electrochemistry, biocatalysis, materials, and Chemical Vapor Deposition (CVD), etc. In addition, glyme are used in numerous industrial applications, such as cleaning products, inks, adhesives and coatings, batteries and electronics, absorption refrigeration and heat pumps, as well as pharmaceutical formulations, etc. However, there is a lack of comprehensive and critical review on this attractive subject. This review aims to accomplish this task by providing an in-depth understanding of glymes’ physicochemical properties, toxicity and major applications.

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Section: Other Applicationsmentioning

confidence: 99%

Glymes as versatile solvents for chemical reactions and processes: from the laboratory to industry

2014

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“…The europium fluorinated β-diketonate complexes have been obtained through a facile synthesis starting from the europium acetate and the ligands. The present approach finds counterparts in the route previously reported for the analogous [Eu(hfa) 3 (diglyme)] complex [ 28 , 38 ] and offers several advantages, such as high yield, synthesis in a single step, low-cost route from commercially available chemicals. Additionally, all the complexes can be handled in air, are non-hygroscopic, soluble in common organic solvents and present high thermal and chemical stability.…”

Section: Resultsmentioning

confidence: 90%

“…Coordination complexes with various metals have been studied. However, surprisingly, although lanthanide (Ln) complexes have been intensively investigated for their luminescent and magnetic properties [ 27 , 28 ], as well as for biological applications [ 29 , 30 , 31 , 32 , 33 ], there are only a few reports on their peculiar NLO properties [ 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 ].…”

Section: Introductionmentioning

confidence: 99%

Luminescent 1,10-Phenanthroline β-Diketonate Europium Complexes with Large Second-Order Nonlinear Optical Properties

et al. 2022

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Substitution of the diglyme ligand of [Eu(hfa)3(diglyme)] (where hfa is hexafluoroacetylacetonate) with a simple 1,10-phenanthroline leads to a six-fold increase of the product μβEFISH, as measured by the Electric-Field-Induced Second Harmonic generation (EFISH) technique. Similarly, [Eu(tta)3(1,10-phenanthroline)] (where Htta is 2-thenoyltrifluoroacetone) is characterized by a large second-order NLO response. Both 1,10-phenanthroline europium complexes have great potential as multifunctional materials for photonics.

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“…Synthesis.-Due to the interesting mass transport properties of M͑hfa͒ n •glyme adducts, [25][26][27][28][29] the synthesis and characterization of low-melting, fluorinated Pr͑III͒ complexes bearing a coordinated polyether has been the initial goal.…”

Section: Resultsmentioning

confidence: 99%

“…The fragmentation mechanisms are almost identical to those already observed in the homologous lanthanide adducts. 25,26,29 The thermal behavior of the present Pr precursors have been fully investigated by thermogravimetric ͑TG͒ analyses. TG profiles depending on the temperature at atmospheric pressure and isothermal curves measured at 20 Torr in purified nitrogen flow are presented in Fig.…”

Section: Resultsmentioning

confidence: 99%

Study of the Thermal Properties of Pr(III) Precursors and Their Implementation in the MOCVD Growth of Praseodymium Oxide Films

Nigro

Toro

Malandrino

et al. 2004

J. Electrochem. Soc.

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A praseodymium adduct, Pr͑hfa) 3 •diglyme ͓(H-hfa ϭ 1,1,1,5,5,5-hexafluoro-2,4-pentandione, diglyme ϭ CH 3 O͑CH 2 CH 2 O) 2 CH 3 )] has been synthesized. It has been applied as a Pr source for the metallorganic chemical vapor deposition ͑MOCVD͒ of praseodymium containing films on silicon substrate and compared with Pr͑tmhd) 3 ͓(H-tmhd ϭ 2,2,6,6-tetramethyl-3,5-heptandione)͔ precursor. Physical and thermal properties of both Pr͑hfa) 3 •diglyme and Pr͑tmhd) 3 precursors have been fully analyzed and their efficacy as MOCVD precursors for the growth of praseodymium oxide films have been fully tested. Depending on the oxygen partial pressure (p O 2 ), different praseodymium oxide phases have been obtained.Complementary metal-oxide-semiconductor large-scale integrated circuits ͑CMOS LSIs͒ are the most popular devices for electronics. High-performance devices, require, however, downsizing of components such as metal-oxide-semiconductor field effect transistors ͑MOSFETs͒. Today, SiO 2 is the major material for MOSFET gate insulator applications. In the near future, equivalent oxide thickness ͑ETO͒ should reach 1 nm and it will become hard to use SiO 2 because of the unacceptable leakage current due to the direct tunneling and consequently higher power consumption. 1 A possible solution to the problem is the replacement of the ultrathin SiO 2 layer with a thicker film of an alternative insulator having higher dielectric constant. 2,3 Rare earth oxides are potential candidates to replace the SiO 2 layer. 4,5 Among the rare earth oxides, praseodymium oxide, Pr 2 O 3 , has not been studied for microelectronic applications so far, despite its high dielectric constant ( ϭ 26-30) 6 and middle bandgap ͑3.9 eV͒. 7 To date, few reports on molecular beam epitaxial ͑MBE͒ growth and pulsed laser deposition of PrO 2 and/or Pr 2 O 3 films on silicon substrates have appeared in the literature. 8-10 Nevertheless the greater complexities of surface topographies and device structures, such as in 3D trench technology, 11,12 require conforming deposition methods, such as metallorganic chemical vapor deposition ͑MOCVD͒, to maintain a high uniform and conformal coverage. Large-scale film growth by MOCVD takes advantages of simpler, less costly equipment, ready scalability, and higher throughput as compared to conventional physical vapor deposition ͑PVD͒ techniques. [13][14][15] Recently, we reported on the MOCVD growth of high quality Pr 2 O 3 films. 16,17 The success of an MOCVD process depends critically on the availability of volatile, thermally stable precursors that exhibit high and constant vapor pressures, because poor performance affects the film properties. Therefore, an accurate knowledge of the physical properties and thermal behavior of precursors is of fundamental relevance for the optimization of processes in the perspective of achieving uniform and reproducible MOCVD film growth.In the present work, we have synthesized and investigated the mass transport properties of a new praseodymium precursor, Pr͑hfa) 3 •diglyme ͓(H-hfa ϭ 1,...

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Europium “Second Generation” Precursors for Metal-Organic Chemical Vapor Deposition: Characterization and Optical Spectroscopy

Cited by 29 publications

References 29 publications

Glymes as versatile solvents for chemical reactions and processes: from the laboratory to industry

Glymes as versatile solvents for chemical reactions and processes: from the laboratory to industry

Luminescent 1,10-Phenanthroline β-Diketonate Europium Complexes with Large Second-Order Nonlinear Optical Properties

Study of the Thermal Properties of Pr(III) Precursors and Their Implementation in the MOCVD Growth of Praseodymium Oxide Films

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