Thin films (100-1000 Å) of vanadium dioxide (VO2) were created by atomic-layer deposition (ALD) on sapphire substrates. Following this, the optical properties were characterized through the metal-insulator transition of VO2. From the measured optical properties, a model was created to describe the tunable refractive index of VO2.
Vanadium dioxide is a material that has a reversible metal-insulator phase change near 68 °C. To grow VO2 on a wide variety of substrates, with wafer-scale uniformity and angstrom level control of thickness, the method of atomic-layer deposition was chosen. This ALD process enables high-quality, low-temperature (≤150 °C) growth of ultrathin films (100-1000 Å) of VO2. For this demonstration, the VO2 films were grown on sapphire substrates. This low temperature growth technique produces mostly amorphous VO2 films. A subsequent anneal in an ultra-high vacuum chamber with a pressure of 7×10-4 Pa of ultra-high purity (99.999%) oxygen produced oriented, polycrystalline VO2 films. The crystallinity, phase, and strain of the VO2 were determined by Raman spectroscopy and X-ray diffraction, while the stoichiometry and impurity levels were determined by X-ray photoelectron spectroscopy, and finally the morphology was determined by atomic force microscopy. These data demonstrate the high-quality of the films grown by this technique. A model was created to fit to the data for VO2 in its metallic and insulating phases in the near infrared spectral region. The permittivity and refractive index of the ALD VO2 agreed well with the other fabrication methods in its insulating phase, but showed a difference in its metallic state. Finally, the analysis of the films' optical properties enabled the creation of a wavelength- and temperature-dependent model of the complex optical refractive index for developing VO2 as a tunable refractive index material.
Vanadium dioxide undergoes a crystalline phase transition near 68 °C. This produces a structural crystal change from monoclinic to tetragonal. The origin of this transition remains controversial1, however recent research is helping develop an understanding of the processes that produce this transition2,3,4 . Irrespective of the origin, the phase transition changes the optical properties of VO2 from an insulator (transmitting light) at room temperature to a more metallic material (reflecting and absorbing light) above the transition temperature2.
A variety of methods have been used to fabricate VO2 in the past (sputtering, physical vapor deposition, chemical vapor deposition, molecular beam epitaxy, solution, etc.)5. The properties of VO2 largely depend on the technology used to fabricate the films6, which has produced significant variability between different growth techniques and subsequent anneal and led to varying crystallinity and film properties. This work investigates the optical properties of atomic layer deposited (ALD) grown films, however, the approach is applicable to modeling all types of VO2 films.
Recently, groups are constructing optical devices by incorporating thin films of VO2 onto optical substrates. As a rapidly growing new deposition method, ALD can assist in fabricating these optical devices and has several advantages over alternative techniques, such as large-area uniformity, angstrom level thickness control, and conformal film coverage7,8,9. ALD is the preferred technique for applications requiring a self-limiting layer-by-layer deposition approach, fabrication on a wide variety of substrate materials (e.g., for heterogeneous integration), or conformal coating of 3D structures10. Finally, the conformal coating of 3D structures of ALD process is particularly useful in optical applications.
For the experiments in this paper, ultrathin, amorphous ALD films were grown on double-side-polished, c-plane sapphire substrates at low temperatures and annealed in an oxygen environment to produce high-quality crystalline films. Using the experimental measurements, a model is created for temperature and wavelength dependent optical changes in VO2 to enable its use as a tunable refractive index material11.
Caution: Consult all relevant material safety data sheets (MSDS) before use, and follow all appropriate safety practices and procedures. The atomic layer deposition growth of vanadium dioxide uses an ALD reactor. The precursors used for the ALD growth are tetrakis(ethylmethylamido)vanadium(IV) (TEMAV) and ozone (generated from ultra-high purity, UHP, 99.999% oxygen gas at 0.3 slm flow and 5 psi backing pressure). In addition, UHP (99.999%) nitrogen gas is used for purging the reactor chamber. For the subsequent vacuum anneal, UHP oxygen gas is used during annealing and UHP nitrogen for venting. TEMAV is flammable and should only be used with appropriate engineering controls. Compressed oxygen gas is a hazard and should only be used with appropriate engineering controls. Compressed nitrogen gas is a hazard and should only be used with appropriate engineering controls. All gases (TEMAV, oxygen, ozone and nitrogen) are connected to the ALD reactor using appropriate engineering safety controls. Stainless steel tubing connects the ozone generator to the ALD reactor, since it is cleaner and more reliable then plastic tubing. Separate UHP oxygen and nitrogen sources are connected to the vacuum annealing chamber using appropriate engineering safety controls before beginning the procedure. Acetone and 2-propanol are irritants and should only be used with appropriate personal protective equipment and safety procedures (e.g., gloves, fume hood, etc.)
1. Atomic Layer Deposition of Vanadium Dioxide on Sapphire Substrates
2. Annealing
NOTE: VO2 films grown by the ALD technique in step 1 produce amorphous VO2. To create oriented polycrystalline VO2 films, the samples are annealed in a custom ultra-high vacuum annealing chamber with a six-way cross. To keep the annealing chamber clean, a load lock is created to insert and remove samples. A 3" diameter oxygen resistant heater is composed of a custom platinum wire heater. This heater provides radiative heating of an oxidized Inconel sled, to which the samples are mounted. The sled has high emissivity for good heat transfer from the heater to the samples.
3. Characterization
4. Modelling Optical Constants (Permittivity and Refractive Index)
To identify the quality of the ALD grown vanadium oxide, X-ray photoelectron spectroscopy (XPS) was performed on the as-deposited, primarily amorphous VO2 films (Figure 1) as well as annealed crystalline VO2 films (not shown). X-ray diffraction (XRD) was performed on the annealed VO2 films (Figure 2). In addition, to help quantify the vertical profile of the chemistry within the film, depth profiling was performed with a cluster ion source to minimize preferential etching of cation/anion species. Two representative traces are shown in Figure 1, one at the surface and one in the bulk. The depth profile and subsequent XPS measurements show that the top 1-nm of the as-deposited film is not VO2 due to excess environmental (adventitious) oxygen and carbon, but after a more controlled annealing procedure in low-pressure oxygen even the surface stabilizes to VO2. X-ray diffraction measurements were performed with a Cu K-alpha X-ray energy source and show, in Figure 2, a single VO2 peak at 39.9˚. The signature of this peak verifies the quality of the ALD-grown VO2 as well as that the (020) crystal orientation aligns with the sapphire substrate's peak.
To analyze the crystallinity, phase, and strain, Raman spectroscopy was performed using a 532-nm laser for excitation. Figure 3 shows a Raman spectrum of the VO2 film and shows narrow peaks which indicate high crystalline quality. In addition, the increased energy in the vanadium-vanadium low-frequency phonons (193 and 222 cm-1) and the 612 cm-1 mode, as well as the decreased energy of the 389 cm-1 mode, suggest tensile strain in these films12,13.
The morphology was observed by atomic force microscopy (AFM). Figure 4 shows crystal grain sizes on the order of 20-40 nm and a root-mean-square (RMS) roughness of 1.4 nm for as-deposited films (Figure 4A) and an RMS roughness of 2.6 nm for annealed films (Figure 4B).
Optical transmittance and reflectance data were obtained using a white light source with a scanning monochromator and a photodetector, which provided coverage in the visible and near infrared region. Figure 5 shows the temperature dependence of the film as it transitions from an insulator to a metal, demonstrating a transition temperature of 61 °C. Analyzing the experimental data enables the modeling of the temperature and wavelength dependent permittivity of the VO2 as it transitions from insulator to metal. Figure 5 shows how the model accurately predicts the optical behavior when using the parameters in Table 1.
Figure 1: Representative XPS measurements of 35-nm thick VO2 on c-Al2O3. XPS shows that the bulk of the film is VO2 while the surface, which contains C and O contaminates, is shifted more towards V2O5. Stoichiometry suggests VO2. Please click here to view a larger version of this figure.
Figure 2: XRD measurements of 35-nm thick VO2 on c-Al2O3. This XRD measurement shows a single VO2 peak at 39.9˚ that independently verifies the crystal quality and demonstrates the monoclinic (020) orientation is aligned with the underlying sapphire peak. Please click here to view a larger version of this figure.
Figure 3: Raman spectra of VO2 on c-Al2O3. This Raman spectrum has narrow peaks, indicating high crystalline quality, and shows a slight tensile strain. Please click here to view a larger version of this figure.
Figure 4: Morphology of VO2 on c-Al2O3. The AFM images show uniform, continuous films with grain sizes on the order of 20-40 nm and RMS roughnesses of (A) 1.4 nm for the as-grown film and (B) 2.6 nm for the annealed film. Please click here to view a larger version of this figure.
Figure 5: Near-infrared optical transmittance and reflectance of 35-nm thick VO2 on c-Al2O3. The temperature-dependent behavior of the optical transmittance and reflectance of vanadium dioxide film are show at 40, 60, 70, and 90 °C. The open circles in the plot are the measured transmittance, reflectance, and calculated absorptance of the VO2 on sapphire structure at various temperatures, while the solid lines are the predicted values from the two-dimensional temperature- and wavelength-dependent model of VO2. Please click here to view a larger version of this figure.
ε∞ | osc. 1 | osc. 2 | ||
Insulator | ||||
3.4 | En | 3.8 | 1.2 | |
An | 33 | 2.1 | ||
Bn | 1.4 | 1.3 | ||
Metal | ||||
4.5 | En | 3.2 | 0.6 | |
An | 13 | 5.3 | ||
Bn | 1.1 | 1 |
Table 1: Representative model parameters for VO2. These parameters are representative of those used in an oscillator model to estimate the permittivity of VO2 in its metallic and insulating phases.
The growth methods described here provide reproducible results with regards to uniformity, chemistry, structure, and morphology. The vanadium precursor is critical to producing the correct stoichiometry of as-deposited ALD films. This particular precursor promotes the +4 vanadium valence state, unlike many of the others listed in the literature that promote the more common +5 valence state. Additionally, this particular precursor has a fairly low vapor pressure and requires heating to provide a sufficient dose to saturate under the conditions given. Since this precursor starts to degrade around 175 °C, this sets an upper temperature limit to both heating of the precursor and ALD growth. Another critical aspect to achieving correct stoichiometry is the ozone concentration (~125 mg/L here) during dosing. Often the concentration of ozone produced by a generator under particular conditions degrades or drifts over time. If this happens, the ozone pulse and purge durations will have to be adjusted to maintain stoichiometry, morphology, and wafer uniformity. What is described here is how to grow ALD VO2 on c-plane sapphire substrates, which includes in-situ ozone pre-treatment. The steps prior to growth for cleaning and nucleation are dependent on the substrate; however, the process described here works for most substrates (inert, oxides, metals, etc.) To determine the best termination cleaning and preparation for VO2 growth, one should consider reactivity between species termination and the vanadium precursor while minimizing any native oxide on the substrate. Finally, this process has been demonstrated on high aspect ratio substrates (up to ~100) but for extreme cases, one should consider an exposure or static ALD method to enhance conformality further.
The ability to achieve high quality, crystalline ALD VO2 films is quite dependent on the post-deposition annealing parameters. The most critical aspect is the pressure, specifically the partial pressure of oxygen. High oxygen pressures lead to faceting and grain growth, eventually causing nanowire formation, as well as results in the V2O5 phase. If the oxygen pressure is too low, oxygen is annealed out of the films resulting in V2O3 phase. Thus, to maintain the correct phase and minimize film roughness, the oxygen pressure should be maintained in the range of 1×10-4 to 7×10-4 Pa. Similarly, the temperature is critical to both being able to crystallize the film, maintain stoichiometry, and minimize roughening of the film. While the temperature of the VO2 film is difficult to measure, empirical findings suggest that crystallization requires stage temperatures greater than 500 °C. At higher temperatures, it is harder to maintain the correct stoichiometry and phase and produce pinhole free films. There is also a trade-off between temperature and anneal time, specifically higher temperatures can reduce the anneal time. Additionally, the anneal duration is directly tied to the thickness of the film. Thicker films require longer times to achieve maximum crystallization. Thus, the oxygen pressure, anneal temperature, and anneal time described in the methods above were optimized to produce high quality VO2 films that exhibit the largest change in optical properties at a nearly ideal transition temperature. Finally, the ramping and cooling rates during the oxygen anneal have an effect on roughness and morphology; the slower these are, the smoother the films.
ALD deposition and subsequent anneal of VO2 produces oriented polycrystalline films with large area uniformity. ALD offers conformally grown films on three-dimensional nanoscale morphologies of almost any substrate. This enables VO2 integration into novel applications, and is especially well suited for optical devices.
Following growth and optical measurements, a model is created which provides a good fit to the data for both the transmittance and reflectance of VO2 in its metallic and insulating phases in the near infrared spectral region (R2 = 0.96-0.99). The reflectance of the infrared insulating phase is the most challenging process in creating this model. Additional oscillator terms were added, but this increased model complexity, only marginally improve the fit in this region. It should be noted that in this model, the superposition of Lorentz oscillators is a common optical model and do not necessarily correspond to specific electronic transitions. Initially, the models included a Drude term, however, after mathematical optimization, the Drude term was essentially eliminated. For this reason, several minimization techniques were examined. However, these different techniques converged upon similar solutions that did not involve a Drude term. The absence of a Drude term in the ALD VO2 could be due to a number of factors, such as 1) doped-semiconductor-like resistivity, or 2) a plasma frequency shift to lower energies and/or large collision rate (damping term), in agreement with the metallic properties of these films.
In the insulating phase, T<60 °C, the permittivity and refractive index of the ALD VO2 agree well with the other fabrication methods (sputtered4,20,21 and pulsed-laser deposition22,23). In the metallic state, T>70 °C, these ALD films exhibit lower loss than the VO2 fabricated by other methods. It is important to note that while different fabrication methods produce somewhat different values for the permittivity and refractive index of VO2, all films show similar trends.
The model in this paper of the temperature and wavelength dependence of the optical permittivity and refractive index agrees well with the experimentally measured data. This model's ability to produce a good quality fit to the measured optical data demonstrates it can reliably predict the optical properties of VO2 as the phase changes from an insulator to a metal. Using these models, the optical properties of VO2 can be predictably tuned by temperature, thickness, and wavelength to design optical systems that achieve static and dynamic goals. These models enable the design and development of optical systems using VO2 in passive and active systems by modifying the film's thickness as well as temperature.
The authors have nothing to disclose.
This work was supported by core programs at the U.S. Naval Research Laboratory.
c-Al2O3 | |||
UHP Oxygen | Air Products | ||
UHP Nitrogen | Air Products | ||
Tetrakis(ethylmethylamido)vanadium(IV) (TEMAV) | Air Liquide | ||
Acetone | Fischer Scientific | A18-4 | |
2-propanol | Fischer Scientific | A416P-4 | |
Savannah S200-G2 | Veeco – CNT | Savannah S200-G2 | |
ozone generator | Veeco – CNT | ozone generator | |
Platinum wire heater | HeatWave Labs | custom |