MOCVD is a suitable technique for the synthesis of functional metal oxide thin films. In the present paper, injection-MOCVD was proved to be an efficient method, not only to grow single layers, but also heterostructures and superlattices of functional oxide materials. We report on the deposition of BaxSr1−xTiO3 (BST) films and BaTiO3/SrTiO3 superlattices [(BTO/STO)n] obtained by injection MOCVD. In a first step, BST films were deposited on various substrates such as LaAlO3(LAO)(012), SrTiO3:Nb(STO:Nb)(001) and Al2O3(0001), resulting in epitaxial films in the case of STO or LAO substrates and highly textured films in the case of Al2O3 substrates. The good crystallinity of the films obtained was evidenced using X-ray analysis. Concerning the dielectric properties of BST films on STO:Nb, the Tc values were found to be the same as those for bulk materials. In a next step the feasibility of (BTO/STO)n superlattices was studied. The multilayers obtained were epitaxially grown on LAO and STO:Nb substrates. XPS was used to check in detail the pattern repetition of the superlattice and proved the low interface roughness of 1 nm as well as the absence of carbon contamination in the film. The measured periodicity of these superlattices were found to be in good agreement with simulation experiments. Further superlattices have been obtained by combining ferroelectric, magnetic (CMR) and superconducting (HTS) oxides. Typical results of these superlattices will be reported.

Injection MOCVD: ferroelectric thin films and functional oxide superlattices

Thickness dependence on the dielectric properties of BaTiO3/SrTiO3-multilayers

High-speed epitaxial growth of SrTiO3 films on MgO substrates by laser chemical vapor deposition

A variety of deposition techniques are employed for ferroelectric thin film capacitors to be used in memory devices. These include sputtering [382], MOCVD (Metal-Organic Chemical Vapour Deposition) [383], MOD (MetalOrganic Decomposition) [384], PLD (Pulsed Laser Deposition) [385], solgel (solution—gelation) spin-on techniques [386], and a mist deposition in which stoichiometrically correct submicron droplets are sprayed into the deposition chamber [387]. The MOCVD techniques include a flash process [388, 389, 390, 391, 392] in which the precursor solutions are delivered to the deposition chamber in liquid form (due to their low volatilities) and then flashed into the vapour phase via incandescent lights or laser sources at a shower head delivery point just below the wafer. These flash systems all differ from each other (Isobe’s achieves the highest deposition rate), and all have separate patents. What they share is the ability to handle viscous precursors with low vapour pressures. [The LG Semiconductor Corp. flash process for BST utilizes relatively viscous barium- and strontium-(THD)2-tetraglyme, together with Ti(O-iso-Pr)(THD)2.] True CVD is not used; that is, vapour deposition with chloride or hydride precursors, since halogen contamination is a problem. MBE (Molecular Beam Epitaxy) is generally not used, with one or two research exceptions [393]. And thick film techniques such as spray pyrolysis, slip-casting, etc., are not used.

Deposition and Processing

High-speed Epitaxial Growth of (110) SrTiO3 Films on (110) MgAl2O4 Substrates using Laser Chemical Vapour Deposition

Injection MOCVD of BaTiO3/SrTiO3 artificial superlattices

BaTiO 3 (BTO) and SrTiO 3 (STO) layers were deposited by injection MOCVD using both a mixed Ba 2 Ti 2 precursor (dissolved in hexane) and a Sr(thd) 2 , Ba(thd) 2 and Ti(OPr) 2 (thd) 2 precursor system (dissolved in monoglyme). Films have been deposited at different temperatures between 600°C and 850°C. The microstructural properties of the films obtained on different kinds of substrates MgO (100). LaAlO 3 (012), sapphire (1-102), Si (100), Pt on Si and YBa 2 Cu 3 O 7 (YBCO) on LaAlO 3 are compared.

Microstructure of BaTiO3 and SrTiO3 layers obtained by injection MOCVD

Superconducting YBa 2 Cu 3 O 7 thin films have been grown by Injection MOCVD on different kind of monocristalline substrates: MgO, NdGaO 3 , LaAlO 3 with critical current densities Jc(77K) over 10 6 A/cm 2 on all of these substrates and up to 7.10 6 A/cm 2 on LaAlO 3 . Heterostructures have been grown on metallic substrates with convenient YSZ buffer. Biaxially textured YBCO films have been realized with Jc(77K) = 5.10 5 A/cm 2 . Other heterostructures with an active dielectric SrTiO 3 layer have been grown for tunable microwave devices applications with promising properties. Finally Injection MOCVD has shown to be well adapted for the formation of multilayers and superlattices with a control of the layer thickness in the range of one unit cell. YBa 2 Cu 3 O 7-δ /PrBa 2 Cu 3 O 7-δ superlattices have been grown with anisotropic superconducting properties which can be tailored by changing the layer thickness of both superconducting and insulating layer.

MOCVD of superconducting oxides, heterostructures and superlattices

In this paper we report on the deposition of BST films and BaTiO 3 /SrTiO 3 superlattices (BTO/STO) obtained by injection MOCVD. In a first time, BST films were deposited on various substrates such as LaAlO 3 (LAO), SrTiO 3 :Nb(STO:Nb) and Al 2 O 3 (0001), resulting in epitaxial films in the case of STO or LAO substrates and highly textured films in the case of Al 2 O 3 substrates. The good crystallinity of the films obtained was evidenced using X-ray analysis. Concerning the dielectric properties of the BST films deposited on STO:Nb one can mention that the T c values were found to be the same as those for bulk materials. Furthermore, the feasibility of BTO/STO multilayers on Al 2 O 3 (0001) was investigated. The grown superlattices were (111) oriented displaying good crystallinity.

Injection MOCVD of BaTiO3 artificial superlattices

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Injection MOCVD of BaTiO3/SrTiO3 artificial superlattices

Microstructure of BaTiO3 and SrTiO3 layers obtained by injection MOCVD

MOCVD of superconducting oxides, heterostructures and superlattices

Injection MOCVD of BaTiO3 artificial superlattices