Volatile CeIII Hexafluoroacetylacetonate Glyme Adducts as Promising Precursors for the MOCVD of CeO2 Thin Films

Malandrino, Graziella; Nigro, Raffaella Lo; Benelli, C.; Castelli, Francesco; Fragalá, Ignazio L.

doi:10.1002/1521-3862(200010)6:5<233::aid-cvde233>3.0.co;2-d

Cited by 40 publications

(31 citation statements)

References 18 publications

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“…Pollard et al 368 designed new glyme-adduct precursors of [Ce(hfac) 3 (glyme)] (glyme = mono-, di-, or tri-) and [(Ce(hfac) 3 ) 2 (μ-tetraglyme)] and used them in the CVD formation of films of cerium oxides on substrates Si, Pt, and TiN. 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.…”

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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“…[20,21] We have recently reported on a novel class of complexes, known as "second-generation" precursors, the framework of which combines fluorinated b-diketonate arrays and ancillary coordinated polyethers, thus providing monomeric, volatile, and thermally stable rare-earth metal sources. [22][23][24][25][26][27] The Ln(hfa) 3 glyme adducts have been widely applied to various materials ranging from the complex perovskitebased oxides such as LaAlO 3 [28][29][30] and La 2-x Ba x CuO 4+d phases, so represent particularly suited single-source precursors for the MOCVD of LnF 3 or LnOF. In this paper, we report on the deposition of lanthanumcontaining films from the single-source MOCVD precursor La(hfa) 3 diglyme (Hhfa = 1,1,1,5,5,5-hexafluoroacetylacetone, diglyme = bis(2-methoxyethyl)ether).…”

Section: Introductionmentioning

confidence: 99%

Effects of Processing Parameters in the MOCVD Growth of Nanostructured Lanthanum Trifluoride and Oxyfluoride Thin Films

Malandrino

Perdicaro

Fragalá

2006

Chemical Vapor Deposition

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Using metal-organic (MO)CVD, lanthanum trifluoride (LaF 3 ) and oxyfluoride (LaOF) films are deposited on Si(100), glass, and quartz from a La(hfa) 3 diglyme single-source precursor. The films are characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM). They are found to be crystalline with a high degree of fiber texture even when deposited on glass or quartz substrates. The SEM indicates very homogeneous surfaces with grain dimensions decreasing upon increasing the deposition temperature and the oxygen flow. The AFM data indicate a very smooth surface with a root mean square (rms) roughness of 0.96 nm for films deposited at high temperature/high oxygen flow.

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“…In addition, ''M͑hfa͒ n '' ␤-diketonates consist of water-coordinated complexes which show a quite low vapor pressure because of H bondings and, even more important, decompose upon heating. Finally, ''M͑hfa) 3 glyme'' adducts already synthesized in the case of other rare earths elements such as La, Ce, Gd, and Eu have been tested [25][26][27][28][29] and proved to be good MOCVD precursors for the deposition of rare earth simple or mixed oxides ͑i.e., CeO 2 and LaAlO 3 ) thin films in a wide range of substrates. [40][41][42] In this context, the synthesis of the new Pr͑hfa͒ 3 •diglyme precursor must be placed.…”

Section: Discussionmentioning

confidence: 99%

“…Note, in this context, that using the Ce͑hfa͒ 3 •diglyme precursor, high quality CeO 2 films have been obtained. 26,40 Therefore, the problem of unwanted fluorinated phases should be addressed time by time, depending on the metallic nature and thermodynamic stability of the desired phase.…”

Section: Discussionmentioning

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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Volatile CeIII Hexafluoroacetylacetonate Glyme Adducts as Promising Precursors for the MOCVD of CeO2 Thin Films

Cited by 40 publications

References 18 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

Effects of Processing Parameters in the MOCVD Growth of Nanostructured Lanthanum Trifluoride and Oxyfluoride Thin Films

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

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