Atomic layer deposition and characterization of vanadium oxide thin films

Blanquart, Timothee; Niinistö, Jaakko; Gavagnin, Marco; Longo, V Valentino; Heikkilä, Mikko; Puukilainen, Esa; Pallem, Venkateswara; Dussarrat, Christian; Ritala, Mikko; Leskelä, Markku

doi:10.1039/c2ra22820c

Cited by 85 publications

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“…The TG weight loss for V(NEtMe) 4 was reported to finish at ;210°C, and its evaporation temperature was set as 65°C during ALD. 28 In our case, V(dma) 4 completed weight loss at a much lower temperature around 160°C, and therefore we expected (validated later) that room temperature should be enough to provide sufficient V (dma) 4 vapor for ALD. Thus, no additional heating is needed for this precursor, which can greatly simplify the design of ALD reactors for future large-scale applications.…”

Section: Resultsmentioning

confidence: 99%

“…This suggested that V(dma) 4 is a highly volatile compound with sufficient thermal stability to serve as a suitable precursor for ALD. Moreover, V(dma) 4 is comparatively much more volatile than V(NEtMe) 4 , a previously reported 28 vanadium precursor which has a similar chemical structure as V (dma) 4 . The TG weight loss for V(NEtMe) 4 was reported to finish at ;210°C, and its evaporation temperature was set as 65°C during ALD.…”

Section: Resultsmentioning

confidence: 99%

“…Similar results were also obtained with the use of V(NEtMe) 4 as the vanadium precursor. 28 It should be noted that the film oxygen content could also be affected by post oxidation after the films were exposed to air, and also, incorporation of water and/or unreacted hydroxyl groups during deposition could deviate the oxygen content from ideal stoichiometry as well. Deconvolution of the high-resolution V 2p 3/2 spectrum [ Fig.…”

Section: Resultsmentioning

confidence: 99%

“…A similar precursor, vanadium n-propoxide, could also be used along with acetic acid to produce ALD V 2 4 ] was described with water or ozone for depositing VO x thin films. [28][29][30] In this case, since metalnitrogen bonds are generally weaker than metal-oxygen bonds in transition metal organic compounds, V(NEtMe) 4 should be more reactive toward forming oxides in ALD. Also, V is in nominal 14 valence state in V(NEtMe) 4 , and it should be therefore more favorable for depositing stoichiometric VO 2 thin films.…”

mentioning

confidence: 99%

“…Over the years, various preparation approaches have been developed for VO x thin films, such as sol-gel, 12 spray pyrolysis, 13 electrodeposition, 14 evaporation, 15 magnetron sputtering, 16 pulsed laser deposition, 17 chemical vapor deposition, 18 and atomic layer deposition (ALD). 6,8,[19][20][21][22][23][24][25][26][27][28][29][30][31][32] Among these approaches, ALD is of particular interest for preparing thin films. ALD employs alternate saturated self-limiting surface chemistry reactions, and allows one to deposit thin films in a well-controlled layer-by-layer fashion.…”

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Atomic layer deposition of vanadium oxide thin films from tetrakis(dimethylamino)vanadium precursor

et al. 2016

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Atomic layer deposition (ALD) of vanadium oxide (VO x ) thin films, using tetrakis(dimethylamino)vanadium as the vanadium precursor, is comprehensively reported in this work. The vanadium precursor is highly volatile and can be used at room temperature for deposition. Either H 2 O or O 3 can be used as the coreactant for depositing VO x at 50-200°C. However, partial precursor decomposition is suggested for the deposition temperature higher than 160°C. The as-deposited VO x films are pure, smooth, and amorphous, and can be crystallized into monoclinic VO 2 phase by postdeposition annealing under N 2 ambient. The minimum annealing temperature for film to crystallize is found, by in situ high-temperature X-ray diffraction experiments, at around 550-600°C. In situ quartz crystal microbalance experiments are performed to further analyze the surface reaction mechanism involved in this ALD process.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Atomic layer deposition of vanadium oxide thin films from tetrakis(dimethylamino)vanadium precursor

et al. 2016

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Atomic Layer Deposition for High‐Efficiency Crystalline Silicon Solar Cells

Macco

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2017

Atomic Layer Deposition in Energy Conversion Applications

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Metal‐Insulator Transition in ALD VO₂ Ultrathin Films and Nanoparticles: Morphological Control

Peter

Martens

Rampelberg

et al. 2014

Adv Funct Materials

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679wileyonlinelibrary.com attractive for potential applications, such as nanoelectronic switches, [3][4][5] transistors, [ 6 ] optical devices, [ 7,8 ] and micromechanical devices. [ 9 ] VO 2 thin fi lms have been synthesized by a variety of deposition techniques, such as pulsed laser deposition (PLD), [10][11][12][13][14] molecular beam epitaxy (MBE), [ 15 ] reactive sputtering, [ 16,17 ] sol-gel processing, [ 18 ] chemical vapor deposition (CVD), [ 19 ] thermal oxidation, [ 20 ] and ion beam deposition. [ 21,22 ] Most of the studies report on VO 2 fi lms with thicknesses in the range of 40-200 nm. Sub-10 nm continuous fi lms of ≈2 nm thickness have been deposited both by PLD [ 23 ] and MBE [ 15 ] on monocrystalline TiO 2 and MITs with resistivity changes of ≈500 × and ≈25 × , respectively. However, the use of TiO 2 monocrystals as a substrate is unfavorable for practical nanoelectronic applications and PLD and MBE are not deposition techniques that are well suited for device manufacturing. By contrast, VO 2 fi lms deposited by techniques suitable for manufacturing, including atomic layer deposition (ALD), have typically been noncontinuous and have shown a strongly degraded MIT when the fi lm thicknesses were below 40-50 nm. [24][25][26] In recent years, ALD [ 27,28 ] has become the reference technique for the deposition of dielectric [ 29 ] and metallic [ 30 ] thin fi lms for nanoelectronic applications. [31][32][33] ALD is characterized by self-limiting surface reactions, which enables a precise control over fi lm thickness and stoichiometry. In addition, the high conformality allows deposition onto three-dimensional (3D) structures, as increasingly required for advanced nanoelectronic applications. However, the ALD growth of thin high quality VO 2 is not established yet. VO 2 ALD has been reported using vanadyl acetonate and O 2 [ 34 ] or VOCl 3 . [ 35 ] X-ray diffraction (XRD) indicated the presence of VO 2 and signs of MITs have been observed. Yet, these processes have not been able to achieve thin, continuous, and phase-pure fi lms. By contrast, the ALD from tetrakis(ethylmethylamino) vanadium (TEMAV) and O 3 has led to continuous smooth fi lms that show an MIT down to a thickness of ≈40 nm. [36][37][38][39] ALD VO 2 from TEMAV with H 2 O as oxygen source has been reported to lead to mixed valence VO x fi lms which can be converted to VO 2 by postannealing. [ 40 ] Nevertheless, no continuous ALD VO 2 fi lms featuring an MIT Nanoscale morphology of vanadium dioxide (VO 2 ) fi lms can be controlled to realize smooth ultrathin (<10 nm) crystalline fi lms or nanoparticles with atomic layer deposition, opening doors to practical VO 2 metal-insulator transition (MIT) nanoelectronics. The precursor combination, the valence of V, and the density for as-deposited VO 2 fi lms, as well as the postdeposition crystallization annealing conditions determine whether a continuous thin fi lm or nanoparticle morphology is obtained. It is demonstrated that the fi lms and particles possess both a structural and an electronic t...

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Atomic layer deposition and characterization of vanadium oxide thin films

Cited by 85 publications

References 36 publications

Atomic layer deposition of vanadium oxide thin films from tetrakis(dimethylamino)vanadium precursor

Atomic layer deposition of vanadium oxide thin films from tetrakis(dimethylamino)vanadium precursor

Atomic Layer Deposition for High‐Efficiency Crystalline Silicon Solar Cells

Metal‐Insulator Transition in ALD VO₂ Ultrathin Films and Nanoparticles: Morphological Control

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Atomic layer deposition and characterization of vanadium oxide thin films

Cited by 85 publications

References 36 publications

Atomic layer deposition of vanadium oxide thin films from tetrakis(dimethylamino)vanadium precursor

Atomic layer deposition of vanadium oxide thin films from tetrakis(dimethylamino)vanadium precursor

Atomic Layer Deposition for High‐Efficiency Crystalline Silicon Solar Cells

Metal‐Insulator Transition in ALD VO2 Ultrathin Films and Nanoparticles: Morphological Control

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Metal‐Insulator Transition in ALD VO₂ Ultrathin Films and Nanoparticles: Morphological Control