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Fan L S, Liu F, Wu G L, et al. Research progress of laser-assisted chemical vapor deposition[J]. Opto-Electron Eng, 2022, 49(2): 210333. doi: 10.12086/oee.2022.210333
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Research progress of laser-assisted chemical vapor deposition
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Abstract
Laser chemical vapor deposition (LCVD) technology has its unique advantages in reducing deposition temperatures, enhancing film purity and directly writing complex thin film patterns compared with conventional chemical vapor deposition (CVD). This technology has been widely applied in thin film deposition and attracted growing attention from both research and industries. This review categorizes the LCVD technology into three types according to the laser-matter interaction mechanisms, including laser pyrolysis, laser photolysis, and laser resonance excitation sensitization. We illustrate the deposition principles governed by the three different mechanisms in detail, and briefly introduce the commonly used equipment, and summarize the latest research progress of LCVD technology in synthesis and applications of metals, carbon-based materials, oxides and semiconductors. The detection and analysis methods used in LCVD are specially introduced, and the challenges and prospects of LCVD in material synthesis are discussed. -
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References
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Overview
Laser chemical vapor deposition (LCVD) is a promising method for selective deposition of solid materials via localized chemical vapor reaction driven by a laser beam. It has several advantages over traditional CVD processes including decreased deposition temperature, increased deposition rate, higher crystallization quality, superior spatial resolution, site-selective deposition characteristics and the ability to produce a wide range of complex 3D micro- and nanostructures. In this review, LCVD is divided into three types based on the interaction mechanisms of laser and gaseous precursor, i.e., pyrolytic LCVD, photolytic LCVD and vibrational excitation LCVD. In pyrolytic LCVD processes, a focused laser beam triggered by a continues CO2 laser or Nd:YAG laser is used to locally heat the surface of the substrate and material deposition occurs when the temperature near the irradiated area reaches the decomposition threshold of the gaseous precursor. This approach is often used to deposit small regions of 2D films with complex and fine patterns. Photolytic LCVD processes use photons from focused laser beams (typically generated by short-wavelength ultraviolet laser light source, such as excimer laser and high frequency output of Nd:YAG laser) to reactant gases, resulting in precise deposition of solid material in either 2D films or 3D structures. Photolytic LCVD processes rely on the photochemical action of the laser beam and the chemical reactants. The precursor gas molecules are directly dissociated by the high-energy photons and subsequently form a solid deposit on the surface of the substrate through recombination/re-decomposition. Photolytic LCVD typically utilizes pulsed lasers as their high peak power levels more effectively to drive the chemical reactions. This method is suitable for large-area film formation. Vibrational excitation LCVD often uses laser sources with adjustable wavelengths, such as infrared CO2 lasers and OPO lasers. By precisely modulating the laser wavelength, the laser energy is directionally coupled to selected gas molecules to induce efficient dissociation of key reaction molecules, resulting in deposition of solid material in a low ambient temperature. Vibrational excitation LCVD typically offers a higher deposition rate and a better film quality compared to the photolysis of the precursors with a UV laser. In this article, we first introduce the deposition principles and commonly used equipment of the three LCVD processes, and then a comprehensive survey of recent material deposition applications using this three LCVD approaches is presented. Finally, the challenges and opportunities in the application of LCVD for material preparation are summarized, and the development prospects of this technology are prospected.
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Fan L S, Liu F, Wu G L, et al. Research progress of laser-assisted chemical vapor deposition[J]. Opto-Electron Eng, 2022, 49(2): 210333. doi: 10.12086/oee.2022.210333
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Figure 1.
Different relaxation channels for energy transfer during binary collisions of molecules[79]
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Figure 2.
Commonly used experimental setup for pyrolysis LCVD
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Figure 3.
(a) Plot of three regimes for incubation, nucleation and coalescence of W deposited at 2.44 W; (b) Thickness of W films deposited on glass substrates plotted as a function of deposition time; (c) Surface morphology of deposited W films deposited at different laser power[81]
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Figure 4.
SEM images of diamond grown on tungsten surface of (a) poorly and (b) heavily nucleated[96]
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Figure 5.
(a) XRD patterns of the β-SiC films prepared at different laser power, deposition pressure and deposition temperature; (b) Effects of laser power and deposition pressure on preferred crystalline orientations of β-SiC films[97]
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Figure 6.
(a) Surface and (b) cross-sectional SEM images of HfO2 films prepared using conventional CVD at 1173 K, (c), (e) surface and the corresponding (d), (f) cross-sectional SEM images of (c), (d) HfO2 films prepared at 1203 K and (e), (f) HfO2 films prepared at 1383 K by pyrolysis CVD, effect of deposition temperature on deposition rate, crystallite size, and morphological evolution in HfO2 films prepared using (g) conventional CVD and (h) pyrolysis CVD[71]
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Figure 7.
Surface and cross‐sectional SEM images of the SrTiO3 films prepared at 760 K (a, b) , 957 K (c, d) and 1104 K (e, f) with a laser power of 150 W, respectively; (g) Influences of the deposition temperature on thickness, grains size, grains shape, and preferred orientation of the SrTiO3 films[128]
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Figure 8.
(a), (b) TEM observations and (c) atomic configuration of the nanoforest-like 3C-SiC/graphene composite films deposited at 1523 K and 400 Pa, (d) schematic illustration and (e) cycling performance of 3C-SiC/graphene nanoforest composite films with stable framework and continuous electron pathways[136]
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Figure 9.
Commonly used experimental setup and principle of photolysis LCVD
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Figure 10.
SEM photographs and corresponding 3D images of the deposited tungsten patterns for various laser power.
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Figure 11.
(a) Surface and cross-sectional SEM images of diamond films prepared at different laser energy densities; (b) The reaction process diagram of active species in the combustion flame under the ultraviolet light irradiation[61]
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Figure 12.
Surface image surface and cross-sectional SEM images of TiNx films prepared at Tpre = 423 K with varied laser power.
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Figure 13.
Si3N4 film prepared by LVCD.
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Figure 14.
Commonly used experimental setup for laser resonant excitation LCVD
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Figure 15.
The influence of laser resonant excitation on CVD of carbon nano-onions.
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Figure 16.
BDD prepared using resonant excitation LCVD method and their electrochemical performance in glucose tests.
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Figure 17.
(a, b) Cross-sectional SEM images of GaN films and (c, d) XRD patterns of GaN grown at different temperature in LMOCVD and conventional MOCVD process, respectively[54]
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Figure 18.
(a) Experimental setup for the CO2 laser-assisted CCVD and (b) optical emission spectra and (c) mole fractions of the species of NH3/C2H2/O2 flames under different laser excitations measured using mass spectrometer[181]; (d) Optical images of C2H4/C2H2/O2 flames[184]
- Figure .
