Vanadium dioxide-based optical and radiofrequency switches
10649240 ยท 2020-05-12
Assignee
Inventors
- Zhenqiang Ma (Middleton, WI, US)
- Chang-Beom Eom (Madison, WI, US)
- Jaeseong Lee (San Jose, CA, US)
- Daesu Lee (Madison, WI, US)
- Sang June Cho (Fitchburg, WI, US)
- Dong Liu (Madison, WI, US)
Cpc classification
G02F1/0054
PHYSICS
International classification
G02F1/00
PHYSICS
Abstract
Switches for electromagnetic radiation, including radiofrequency switches and optical switches, are provided. Also provided are methods of using the switches. The switches incorporate layers of high quality VO.sub.2 that are composed of a plurality of connected crystalline VO.sub.2 domains having the same crystal structure and orientation.
Claims
1. A heterostructure comprising: a substrate; a layer of VO.sub.2 on the substrate, wherein the layer of VO.sub.2 and the substrate are joined at an epitaxial interface; and a layer of single-crystalline silicon bonded to the layer of VO.sub.2, such that the layer of VO.sub.2 is disposed between the substrate and the layer of single-crystalline silicon, wherein the layer of single-crystalline silicon and the layer of VO.sub.2 are not joined at an epitaxial interface.
2. The heterostructure of claim 1, wherein the layer of single-crystalline silicon is bonded to the layer of VO.sub.2 via an adhesion promoting layer or a planarization layer.
3. The heterostructure of claim 1, wherein the layer of single-crystalline silicon and the layer of VO.sub.2 are in optical communication.
4. The heterostructure of claim 1, wherein the layer of single-crystalline silicon and the layer of VO.sub.2 are in electrical communication.
5. A structure comprising: a substrate; a layer of VO.sub.2, wherein the layer of VO.sub.2 comprises a plurality of connected crystalline VO.sub.2 domains having the same crystal structure and epitaxial orientation; and a layer of single-crystalline silicon on a surface of the layer of VO.sub.2, wherein the layer of VO.sub.2 is disposed between the substrate and the layer of single-crystalline silicon.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) Illustrative embodiments of the invention will hereafter be described with reference to the accompanying drawings, wherein like numerals denote like elements.
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DETAILED DESCRIPTION
(16) Switches for electromagnetic radiation, including radiofrequency switches and optical switches, are provided. Also provided are methods of using the switches. The switches incorporate layers of high quality VO.sub.2 that are composed of a plurality of connected crystalline VO.sub.2 domains having the same crystal structure and epitaxial orientation. In the VO.sub.2 layer, the domains are connected to one another by domain boundaries. In contrast, in a cracked single crystal of VO.sub.2, small crystallites are disconnected due to the cracks. The VO.sub.2 has a sharp insulator to metal phase transition (IMT) at temperatures moderately higher than room temperature. The IMT is accompanied by a large decrease in resistively, which makes the VO.sub.2 useful in radiofrequency switching applications. The IMT also decreases the refractive index of the VO.sub.2 and increases its extinction coefficient, which makes the VO.sub.2 useful in optical switching applications.
(17) The VO.sub.2 layer can be grown epitaxially on a symmetrically isostructural SnO.sub.2 template. The lattice mismatch between the VO.sub.2 and SnO.sub.2 produces small, well-connected domains of VO.sub.2 having the same crystal structure in the epitaxial film and confines severe structural defects (e.g., strain gradients and cracks) to the area near the SnO.sub.2/VO.sub.2 interface. This leads to homogeneous, bulk-like lattices in the VO.sub.2 film, without compromising the film's epitaxial nature. This structural homogeneity also enables homogeneous electronic and chemical states throughout the films, which is highly desirable for creating reliable, high performance devices, such as high-speed switches.
(18) The VO.sub.2 in the epitaxial films is characterized by an IMT critical temperature. Below this critical temperature, the VO.sub.2 has an electrically insulating monoclinic crystal structure. As the VO.sub.2 is heated to and above its critical temperature, the crystal structure transitions to a metallic conducting rutile crystal structure. In the VO.sub.2 films, the transition is very sharp and is accompanied by a large decrease in the films' electrical resistance. In addition, the small crystalline domains in the VO.sub.2 films help them to absorb the stresses and strains that accompany the phase transition, enabling the films to undergo many phase transition cycles without cracking. As a result, the VO.sub.2 films are well suited for switching applications.
(19) One embodiment of a layered structure comprising a VO.sub.2 overlayer is shown schematically in
(20) The lattice mismatch between the TiO.sub.2 substrate and the SnO.sub.2 results in the epitaxial, nanoscale, crystalline columnar domains in the SnO.sub.2 growing upward from the TiO.sub.2 growth surface. These domains, which have the same crystal structure (rutile) and orientation, nucleate separately on the growth surface and grow together to form a growth template that is isostructural with the subsequently grown VO.sub.2 at growth temperatures above T.sub.crit. As such, the SnO.sub.2 films and the VO.sub.2 grown on the SnO.sub.2 films, are not polycrystalline films in which a plurality of crystal domains are oriented randomly within the film. As used herein, the term nanoscale columnar domains refers to columnar domains having average cross-sectional diameters that are no greater than 200 nm. This includes columnar domains having average cross-sectional diameters that are no greater than 100 nm; no greater than 50 nm; and no greater than 20 nm. For example, in some embodiments of the SnO.sub.2 films, the columnar domains have average cross-sectional diameters in the range from about 5 nm to about 10 nm. The thickness of the SnO.sub.2 layer is typically in the range from about 100 nm to about 300 nm, but thicknesses outside of this range can be used.
(21) The lattice mismatch between the SnO.sub.2 and the VO.sub.2 limits the size of the epitaxially grown VO.sub.2 domains and concentrates and/or confines any cracks in the VO.sub.2 film to a small volume near the SnO.sub.2/VO.sub.2 interface, while the remainder of the VO.sub.2 may be crack- and strain-free. This is advantageous because it allows the VO.sub.2 layers to be grown to commercially practical thicknesses without any significant cracking beyond the lowermost portion of the layer. By way of illustration only, in some embodiments of the layered structures, the VO.sub.2 layer has a thickness of at least 100 nm. This includes layered structures having a VO.sub.2 layer thicknesses of at least 200 nm and further includes layered structures having a VO.sub.2 layer thicknesses of at least 300 nm. For example, in some embodiments, the VO.sub.2 layer thickness is in the range from about 100 nm to about 500 nm. This includes embodiments in which the VO.sub.2 layer thickness is in the range from about 200 nm to about 400 nm. In each of these embodiments, the cracks and/or strains (if present at all) may be confined to within a few nanometers (for example, 10 nm or fewer, including 5 nm or fewer) of the SnO.sub.2/VO.sub.2 interface.
(22) The small size of the VO.sub.2 domains helps the VO.sub.2 film to absorb the stresses and strains of the IMT, which reduces cracking during phase change cycling and improves and sustains device performance. As used here, the size of the domains refers to the largest cross-sectional width of the domains, where the width dimension is perpendicular to the thickness dimension. In some embodiments of the layered structures, the average width of the VO.sub.2 domains is no greater than about 500 nm. This includes embodiments in which the average width of the VO.sub.2 domains is no greater than about 400 nm and further includes embodiments in which the average width of the VO.sub.2 domains is no greater than about 300 nm. The VO.sub.2 domains are well-connected, have a common crystal structure and an epitaxial relationship with the underlying SnO.sub.2. At temperatures below T.sub.crit, the VO.sub.2 has a monoclinic crystal structure and is electrically insulating. The monoclinic VO.sub.2 domains can have four different rotational domains that are rotated by 90 from each other in the plane of the film. The different rotational domains are represented by area of different shading in overlayer 110 on the right side of
(23) The T.sub.crit for the VO.sub.2 in the overlayer is greater than room temperature (i.e., greater than 27 C.) and is similar to, or the same as, the T.sub.crit for bulk VO.sub.2. Typically, the T.sub.crit is greater than 55 C. and in the range from about 58 C. to about 68 C. (e.g., 60 C. to 66 C.). (Unless otherwise indicated, the phase transition critical temperatures referred to in this disclosure refer to the critical temperature in the absence of an applied external field or strain.)
(24) The high quality VO.sub.2 films grown on SnO.sub.2 template layers can be characterized by their sharp IMTs, where the sharpness of a transition is characterized by the full width at half maximum (FWHM) of the derivative curve of a heating curve, as illustrated in the Examples. Some embodiments of the VO.sub.2 films have a phase transition sharpness of 5 C. or less. This includes VO.sub.2 films having a phase transition sharpness of 3 C. or less and further includes VO.sub.2 films having a phase transition sharpness of 1 C. or less. These sharp transitions can be achieved even in films with thicknesses above 100 nm, above 200 nm, and above 300 nm.
(25) The monoclinic to rutile (insulating to conducting) phase transition is accompanied by a large drop in the vanadium dioxide's magnitude of electrical resistance (R), which can be measured as described in the Examples. Some embodiments of the VO.sub.2 films have a R of at least 2 orders of magnitude. This includes VO.sub.2 films having a R of at least 3 orders of magnitude and further includes VO.sub.2 films having a R of at least 4 orders of magnitude.
(26) Although the switches can retain the SnO.sub.2 template layer and TiO.sub.2 substrate upon which the VO.sub.2 layer is grown, it is also possible to remove one or both of these layers after VO.sub.2 layer growth and before it is incorporated into a switch. The released VO.sub.2 layer can be transferred onto another support substrate, which may be an electrically conducting (metallic), semiconducting, or electrically insulating substrate.
(27) One embodiment of a switch for electromagnetic radiation signals includes an electromagnetic radiation waveguide in electrical and/or optical communication with a layer of the VO.sub.2. The two components can be considered to be electrical communication with one another if a current can flow from one to the other when the VO.sub.2 is in its insulating state, its metallic states, or when it is in either state. Two components that are in electrical communication can be in direct contact, but they need not be. The two components can be considered to be in optical communication with one another if an optical signal can pass from one to the other when the VO.sub.2 is in its insulating state, its metallic states, or when it is in either state. Two components that are in optical communication can be in direct contact, but they need not be.
(28) The waveguide provides a signal line for the transmission electromagnetic radiation. Therefore, the waveguide material will depend on the nature of the radiation to be transmitted. By way of illustration, electrically conductive waveguides having low resistivities can be used as signal lines for the transmission of radiofrequency signals. Suitable materials for radiofrequency (including microwave) waveguides include metals, such as gold, silver, and copper. Optical waveguides, which transmit wavelengths in the infrared region of the electromagnetic spectrum, are typically comprised of dielectric materials with high permitivities. Suitable materials for optical waveguides include silicon. The waveguides can have a variety of dimensions and cross-sectional shapes. However, in some embodiments of the switches, the waveguides are planar or strip waveguides.
(29) The VO.sub.2 layer can be used as a switch by applying an external stimulus to trigger the IMT. For example, heat can be applied to the VO.sub.2 to raise its temperature above its T to trigger the phase transition. However, other external stimuli, such as an electric field, an optical field, a mechanical strain, or a combination thereof, can be applied to the VO.sub.2 to induce the phase transition. These external stimuli shift the critical temperature for the IMT and induce the reversible phase transition, which changes the resistance (and, therefore, conductance) of the VO.sub.2 and modulates the transmission of the electromagnetic waves through the material. An external stimulus can be provided by its corresponding external stimulus source, configured to apply IMT-inducing stimulus to the VO.sub.2 layer. For example, an external heat source can be used to apply heat to the VO.sub.2 layer, an external voltage source can be used to apply an electric bias to the VO.sub.2 layer, and/or a mechanical actuator can be used to apply a mechanical strain to the VO.sub.2 layer.
(30) Some embodiments of the switches, including the radiofrequency switches, utilize the IMT-induced decrease in the VO.sub.2 layer's resistivity and an accompanying increase in the transmission of the electromagnetic signal through the VO.sub.2. Depending on the configuration of the switch, this can correspond to an increase in, or an attenuation of, the electromagnetic signal traveling through a waveguide. Switches that incorporate the VO.sub.2 layers as switching layers include shunt switch configurations and series switch configurations.
(31) A cross-sectional view of one embodiment of a shunt switch is shown schematically in
(32) A top view and a cross-sectional side view of one embodiment of a series switch are shown schematically in the upper and lower parts, respectively, of panel (iii) in
(33) Other embodiments of the switches, including the optical switches (optical modulators), utilize the IMT-induced decrease in the VO.sub.2 layer's refractive index to optical signal absorption by the VO.sub.2, thereby modulating the optical signal propagating through the optical waveguide that is in optical communication with the VO.sub.2. Top views and cross-sectional side views of one embodiment of an optical switch are shown schematically in the upper and lower parts, respectively, of
(34) In some embodiments of the optical switches, the optical waveguide is single-crystalline silicon having a refractive index of approximately 3.4, the insulating VO.sub.2 has a refractive index of approximately 3.1, and the metallic VO.sub.2 has a refractive index of approximately 1.7. Some embodiments of the optical switches have a switching speed of 300 ns or faster. However, other optical waveguide materials can be used, provided that the material is able to transmit the signal and has a higher index of refraction than VO.sub.2 in the wavelength range of interest. By way of illustration, suitable waveguide materials may have a refractive index that is at least about 1.5 times that of VO.sub.2 in its metallic state. This includes materials having a refractive index that is at least about 2 times that of VO.sub.2 in its metallic state.
(35) A method for fabricating a VO.sub.2 based optical modulator is shown schematically in
(36) The VO.sub.2 layer 1410 can be grown epitaxially on a SnO.sub.2/TiO.sub.2 structure 1406/1402 (panel (e)) as described herein and illustrated in the Examples. The VO.sub.2 layer can then be patterned into a switching layer using, for example, a reactive ion etch (panel (f)). Optionally, an electrically conductive planarization and/or adhesion promoting layer 1414 can be formed over the VO.sub.2 switching layer (panel (g)).
(37) Using a transfer stamp, the released silicon layer then can be transferred onto the planarization and/or adhesion promoting layer (panels (d) and (h)). An etch mask then can be formed over the transferred silicon layer (panel (i)). Finally, a waveguide can be patterned into the single-crystalline silicon and contact lines can be deposited over the planarization and/or adhesion promoting layer (panel (j)).
Example 1
(38) In this example, thermally triggered RF switches are demonstrated using the VO.sub.2 thin films on (001) TiO.sub.2 (001) substrate with SnO.sub.2 buffer layer. High quality epitaxial VO.sub.2 thin films were employed to fabricate simple single-pole, single-throw (SPST) type switches that use the change in RF impedance by heating and cooling. The RF switching and power characteristics were measured under various temperatures and demonstrated sharp resistivity changes, with the scattering (S-) parameter S.sub.21 greater than 15 dB at 60 C. and 66 C., when switches were heated up and cooled down, respectively. VO.sub.2 RF switches also completed the transition of S.sub.21 within 3 C. of the IMT temperature and showed a low loss operation frequency of up to 24.2 GHz with a low insertion loss of 1.36 dB and isolation of 17.56 dB at 12.03 GHz, respectively.
(39) The schematic illustration of the fabrication process is shown in
(40) The switching characteristics of the fabricated VO.sub.2 RF switches were measured using an Agilent E8364A performance network analyzer (PNA) with the heating stage to control the sample temperature. Scattering (S) parameters in the frequency range from 45 MHz to 40 GHz were taken. The temperature was carefully controlled from room temperature (25 C.) to high temperature (90 C.) with 1 C. step during the measurement.
(41)
(42) When the dimensions of VO.sub.2 RF switches were designed, the following factors were considered. Firstly, most of the TE field is concentrated in the VO.sub.2 layer, as the magnetic field in CPW is elliptically polarized. Secondly, since the VO.sub.2 layer has a high dielectric constant (8=40.6 at 10 Hz), it effectively reduces radiation losses. Taken together, the optimized CPW structure can be used for high frequency signal switching devices with thermally controlled phase transition of VO.sub.2.
(43) TABLE-US-00001 TABLE 1 25 C. On 90 C. Off Components (Insulator) (Metallic) L.sub.CPW (pH) 79 1650 R.sub.CPW () 1.2 480 G.sub.CPW (S) 800 200 C.sub.CPW (fF) 180 3 G.sub.VO2 (S) 2.5 10.sup.5 2.5 10.sup.2 C.sub.VO2_1 (fF) 30 2 C.sub.VO2_2 (fF) 30 2
(44) The L.sub.CPW, R.sub.CPW, G.sub.CPW, and C.sub.CPW values in Table 1 refer to the equivalent components of the lossy CPW line. The VO.sub.2 layer is represented as G.sub.VO2 for the real part of the loss, and C.sub.VO2_1 and C.sub.VO2_2 as the imaginary part of the loss. When VO.sub.2 RF switches operate at the ON-state, RF signal can be transmitted with the low real part insertion loss (R.sub.CPW) as low as 1.2. On the other hand, when VO.sub.2 RF switches operate at the OFF-state above the phase transition temperature, the VO.sub.2 layer turns into its metallic phase with nearly 4 orders.sup.17 of magnitude lower resistance and thus VO.sub.2 RF switches behave as an attenuator. The reduced resistance of the VO.sub.2 layer at the OFF-state becomes a dominant loss part which is in series with the real losses of CPW line components. As a result, the R.sub.CPW increases to 480, which effectively attenuates the signal. Based on the equivalent circuits, the figure-of-merit of the RF switch, the cut-off frequency (F.sub.co), is calculated based on the following equation (1).sup.22,
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where, R.sub.on and C.sub.off are the resistance at the ON-state and the capacitance at the OFF-state, respectively. In this calculation, a R.sub.on of 1.2 and C.sub.off 710.sup.15 F were used and yielded a F.sub.co value of 18.9 THz.
(46) The S.sub.21 value as a function of temperature in the range from room temperature to 90 C. is shown in
(47) In conclusion, thermally triggered normally ON RF switches were demonstrated based on epitaxial VO.sub.2 thin film with a very simple device structure. The high quality epitaxial VO.sub.2 thin film was realized by using an SnO.sub.2 template layer in between the VO.sub.2 layer and TiO.sub.2 substrate. The thin film VO.sub.2 exhibited a similar sharp phase transition to that of the bulk VO.sub.2. A fast insulator-to-metal phase transition at a low temperature allowed VO.sub.2 RF switches to exhibit sharp resistivity changes with the S.sub.2, change greater than 15 dB at 60 C. and 66 C. when switches were heated up and cooled down, respectively. VO.sub.2 RF switches performed the sharp transition of S.sub.21 less than 3 C. and showed a low loss operation frequency up to 24.2 GHz with a low insertion loss of 1.36 dB and isolation of 17.56 dB at 12.03 GHz.
Example 2
(48) In this example, electrically triggered RF switches were demonstrated using the epitaxial VO.sub.2 thin films on a TiO.sub.2 (001) substrate with a SnO.sub.2 template layer. The high quality epitaxial VO.sub.2 thin film was employed to fabricate simple single-pole single-throw (SPST) type switches. DC characteristics of the VO.sub.2 RF switches were measured and compared to RF switching performances of switches through heat and voltage bias. The electrical IMT was also measured by a continuous square wave voltage bias and characterized the switching speed of the VO.sub.2 RF switches.
(49)
(50) After device fabrication, the electrical characteristics were measured using the HP 4155 semiconductor parameter analyzer in ambient air.
(51) The switching performance of the VO.sub.2 RF switches was characterized by measuring scattering (S-) parameters under the frequency range from 45 MHz to 40 GHz using the Agilent E8364A performance network analyzer (PNA). The VO.sub.2 RF switches were tested and compared for both thermal and electrical triggers. A temperature-controlled stage was used for thermally triggered VO.sub.0 RF switch measurements. In order for the VO.sub.2 to be in a fully metallic phase, the sample temperature was increased to 90 C., which is above the phase transition temperature of 68 C. for VO.sub.2. To measure electrically triggered VO.sub.2 RF switches, a 15 V DC bias was applied to the VO.sub.2 RF switches in series with a 1 k resistor via a bias T using the HP E3631A power supply. Also, the VO.sub.2 RF switches were simulated with Keysight ADS 2013 momentum.
(52) Measured and simulated RF characteristic of the VO.sub.2 RF switches at the on- and off-states are shown in
(53) To further analyze RF switching characteristics, the two-port equivalent circuit model of the VO.sub.2 RF switches were employed as shown in
(54) TABLE-US-00002 TABLE 2 On Off Components (Metallic) (Insulator) L.sub.VO2 (pH) 555 R.sub.VO2 () 4.6 4.6 10.sup.4 C.sub.SUB (fF) 2.7 C.sub.CONT1 (fF) 15 15 C.sub.CONT2 (fF) 15 15
(55) One of the clear advantages of an electrical triggering method is that the transition can be completed much faster than other triggering methods, such as by heating or by shining light. Considering that the electrical phase transition occurs by current injection followed by joule heating, a theoretical minimum switching time, t.sub.min, for the electrical phase transition can be calculated by using a simple thermal model with the following equation (1),
(56)
where .sub.VO2 is the density of VO.sub.2 (4340 kg m.sup.3), C.sub.VO2 is the heat capacity of VO.sub.2 (690 J kg.sup.1 K.sup.1), volume is the dimension of VO.sub.2 (54 m*10 m*300 nm), T is the temperature change of the film (341 K298 K=43 K), V and I are voltage and current at the phase transition (13.1 V and 7.7 mA, respectively, from
(57) In order to calculate actual phase transition time, the dynamic response measurements under different frequencies were performed by configuring the circuit as shown in
(58) The calculated minimum switching time, t.sub.min, is approximately 4 times smaller than the measured result. Considering that joule heating is not the only factor that affects the phase transition and the actual device temperature increased above the phase transition temperature, the calculated result is acceptable. However, this result is still several times faster than poly-crystal VO.sub.2-based RF switches. Since both V.sub.IMT and t.sub.IMT are highly dependent on the dimension of the VO.sub.2, the switching speed can be further enhanced by engineering the geometry of the device.
(59) In conclusion, electrically triggered RF switches based on epitaxially grown VO.sub.2 thin films with a simple device structure were demonstrated. The high quality epitaxial VO.sub.2 thin film was achieved using an SnO.sub.2 template layer in between the VO.sub.2 layer and TiO.sub.2 substrate, which enabled it to perform a resistance change of 4 orders of magnitude by electrical triggering. The VO.sub.2 RF switches exhibited an S.sub.21 difference greater than 30 dB at 24.3 GHz by electrical triggering, which implies that electrical IMT is comparable to other IMT approaches. The VO.sub.2 RF switches also showed high frequency responses of insertion losses of 3 dB at the on-state and return losses of 4.3 dB at the off-state over 27 GHz. The study on electrical IMT dynamics revealed 840 ns of phase transition time. The epitaxial VO.sub.2-based RF switches demonstrated high-frequency response and fast transition time.
Example 3
(60) This example reports new template engineering that utilizes an intermediate SnO.sub.2 layer for growing epitaxial VO.sub.2 films and controlling their IMT dynamics. SnO.sub.2 is insulating and has a rutile structure, which makes it as an appropriate template for VO.sub.2. Particularly, the SnO.sub.2 template was adopted because of its large lattice mismatch (i.e., 4.2%) with VO.sub.2, contrary to conventional thin-film epitaxy that prefers a lattice-matched substrate or template. The huge lattice mismatch would lead to an incoherent interface with abrupt strain relaxation and uniform bulk-like lattices in epitaxial VO.sub.2 films (
(61) The lattice strain was examined in VO.sub.2 films, using X-ray diffraction reciprocal space mappings (RSMs).
(62) To obtain further information, a high-resolution, real-space strain mapping was conducted using dark-field inline electron holography (
(63) In-situ transmission electron microscopy (TEM) was used to visualize the phase transition dynamics in epitaxial VO.sub.2 films in real time.
(64) Differently from the VO.sub.2/TiO.sub.2 film, however, the VO.sub.2/SnO.sub.2/TiO.sub.2 film showed a much sharper and homogeneous phase transition.
(65) Interestingly, the in-situ nanoscale imaging (
(66) Given the observed sharp and homogeneous SPT, a sharp IMT in the VO.sub.2/SnO.sub.2/TiO.sub.2 film was expected. The IMT was characterized in epitaxial VO.sub.2 films by measuring electrical resistivity as a function of temperature (
(67) The VO.sub.2/SnO.sub.2/TiO.sub.2 film was shown to undergo sharp and homogenous IMT with varying temperature. Another way for triggering the IMT is to apply external electric field. Applying an electric field to VO.sub.2 drives carrier injection and then induces the formation of a local metallic path in VO.sub.2 on a short time scale of <1 us. However, after the metallic path forms locally, the electric field falls and a thermal process by Joule heating follows with the relation, T 1exp(t/), where r is a time constant. When the electric field is removed, the reverse metal-to-insulator transition is also governed by a cooling process with T exp(t/). These indicate that the switching speed in VO.sub.2 could generally be limited to thermal processes (e.g., thermal transition width T of IMT). Thus, the sharp IMT (i.e., narrow transition width T) in VO.sub.2/SnO.sub.2/TiO.sub.2 film would naturally allow a fast switching by electric field (i.e., small switching time t).
(68) To evaluate the switching speed and device applications, an electrically switchable optical waveguide, i.e., optical modulator, was designed, composed of Si single crystal and epitaxial VO.sub.2 film (
(69)
(70) Template engineering for epitaxial VO.sub.2 films has been demonstrated as a route for controlling the IMT dynamics and achieving sharp and large IMT above room temperature. This example provides the nanoscale visualization of phase transition dynamics in epitaxial VO.sub.2, which reveals not only the critical role of local lattice strain, but also the minor effect of domain/grain boundaries on the IMT dynamics, contrary to conventional belief.
(71) Thin Film Growth.
(72) The epitaxial VO.sub.2 thin films were grown on a (001) TiO.sub.2 substrate using the pulsed laser deposition (PLD) method. Before deposition, low miscut (<0.1) TiO.sub.2 substrates were cleaned by sonicating with acetone and then rinsing with isopropanol. A SnO.sub.2 epitaxial layer with a thickness of 100 nm was deposited as a bottom template on the TiO.sub.2 substrate. A KrF excimer laser (=248 nm) beam was focused on SnO.sub.2 and V.sub.2O.sub.5 ceramic targets to an energy density of 2.0 J cm.sup.2 and pulsed at 5 Hz (for the SnO.sub.2 layer) or 10 Hz (for the VO.sub.2 layer). The SnO.sub.2 layer was grown at a substrate temperature of 400 C. and oxygen partial pressure of 50 mTorr. After the growth of the SnO.sub.2 layer, the VO.sub.2 layer was grown at a temperature of 400 C. and an oxygen partial pressure of 18 mTorr. After growth, the VO.sub.2 films were cooled down to room temperature at an oxygen partial pressure of 18 mTorr.
(73) XRD Measurements.
(74) The structural quality of the films was examined using a high-resolution four-circle X-ray diffraction (XRD) machine (Bruker D8 advance). XRD patterns of the out-of-plane XRD -2 scan of 300-nm-thick VO.sub.2 films on (001) TiO.sub.2 and SnO.sub.2/TiO.sub.2 substrates showed a clear film peak at 2=64.8 along with the (002) diffraction peaks from the underlying rutile SnO.sub.2 and TiO.sub.2 substrate. The film diffraction peak comes from the (
(75) TEM Sample Preparation and In-Situ TEM.
(76) Samples for cross-sectional TEM were prepared by mechanical grinding to a thickness of 80 m, dimpling to a thickness of less than 10 m. The mechanically polished samples were ion-milled using 3 kV Ar.sup.+ ion beam (PIPS, Gatan), and then a low energy (0.7 kV) Ar.sup.+ ion beam was used to remove the surface-damaged layer. In-situ heating experiments were performed in a field-emission TEM (JEM-2100F, Jeol) operated at 200 kV. The samples were heated up to 363 K with a heating rate of 5 K min.sup.1 using a Gatan double tilt heating holder (Model 652-Ta) and then allowed to cool down to room temperature. Real time movies were acquired during the heating-cooling cycle in dark-field TEM mode to distinguish the monoclinic/rutile phase domains, using a CCD camera (ORIUS 200D, Gatan) at 25 frames s.sup.1.
(77) Inline Electron Holography.
(78) Local strain maps were obtained using inline electron holography. The inline electron holography experiment was performed using a JEOL 2100F, equipped with a 200-kV field emission gun. All images were recorded using a Gatan's GIF Tridiem imaging filter to remove inelastically scattered electrons outside an energy window of 07.5 eV. An objective aperture of 10 m in diameter was placed on the microscope's optical axis for selecting a specific beam. The size of this aperture limited the spatial resolution to 0.8 nm. For the out-of-plane strain mapping, the incident electron beam was tilted in such a way that the excited (002) reflection was aligned parallel to the optical axis of the microscope, where the subscript s denotes the substrate (i.e., TiO.sub.2). The (200) reflection was chosen for mapping the in-plane component of the strain, and the transmitted beam was used for mapping the electrostatic potential. Bright-field (BF) and dark-field (DF) images at defocus values ranging from 8 m to +8 m were acquired exposing a 20482048 pixels fiber-optically coupled UltraScan 1000 FT (Gatan. Inc.) camera for 4 s and 8 s, respectively. In order to avoid the post-growth fluctuation or segregation of indium as a result of intense electron beam irradiation during the TEM imaging, the TEM images were obtained at a low magnification under low electron dose conditions. The 2-D electron phase information was reconstructed from a focal series of BF/DF TEM images using the full resolution wave reconstruction (FRWR) software.
(79) Crack Formation.
(80) The contribution of the SnO.sub.2 template to protect the VO.sub.2 films against cracking was explored. VO.sub.2 bulk crystals and epitaxial films tend to crack during phase transition and degrade upon repeated cycling. During SPT on cooling, the rutile phase becomes monoclinically distorted with the formation of monoclinic domains. The domain formation simultaneously causes strong internal stress near domain boundaries, whose value may locally exceed a critical strength and causes cracking, especially in the case of large-sized single crystals. Therefore, it was expected that such crack formation could be avoided in epitaxial VO.sub.2 films that are composed of small grains in their as-grown state.
(81) Cracks were found to be increasingly formed upon repeated thermal cycles and severely affected the IMT features in VO.sub.2 films on bare TiO.sub.2. The increase of resistance by cracks was more significant for the nominally metallic phase and, as a result, the magnitude of resistance change across the IMT was greatly reduced, down to 10.sup.5%. On the other hand, the VO.sub.2 films on SnO.sub.2/TiO.sub.2 showed quite robust IMT, whose magnitude of resistance change remained well conserved as 10.sup.6% even after 1,000 cycles.
(82) Phase Diagram Calculation.
(83) According to the Landau theory, the phase transition in VO.sub.2 can be described by structural order parameters , with =0 and 0 representing the rutile and monoclinic phases, respectively. The total free energy density is given by
f=A.sub.2.sup.2+A.sub.4.sup.4+A.sub.6.sup.6+c.sub.ijkl(.sub.ij.sub.ji.sup.0)(.sub.kl.sub.kl.sup.0),(S1)
where A.sub.2, A.sub.4, and A.sub.6 are coefficients of the Landau polynomial under stress-free boundary conditions, co is the elastic stiffness tensor, and .sub.ij and .sub.ij.sup.0 are the total strain and eigen strain, respectively. The eigen strain is related to the structural order parameter through .sub.ij.sup.0=.sub.ij.sup.00.sup.2, where .sub.ij.sup.00 is the stress-free transformation strain from the rutile to monoclinic phase transition. Among all the coefficients, only A.sub.2 is assumed to be dependent on temperature, i.e., A.sub.2=A.sub.0[TT.sub.c], where A.sub.0 is a constant and T.sub.c is the Curie temperature. In the calculation, A.sub.0=1.4210.sup.6 N m.sup.2, T.sub.c=325 K, A.sub.4=7.1210.sup.6 N m.sup.2, A.sub.6=5.3410.sup.7 N m.sup.2, Young's modulus E=155 GPa. Poisson's ratio v=0.287, and .sub.ij.sup.00 takes the value from Gu Y., Cao J., Wu J. & Chen L.-Q. (See, Thermodynamics of strained vanadium dioxide single crystals. J. Appl. Phys. 108, 083517 (2010).)
(84) The strain-temperature phase diagram was obtained by applying the thin film boundary conditions, i.e.,
(85)
where .sub.s is the biaxial epitaxial strain. Equation (S2) indicates that .sub.s is fixed by the substrate, with the out-of-plane direction stress-free. Through minimizing the free energy density in Eq. (S1) under the thin-film boundary conditions, the stable phases can be calculated at different temperatures and epitaxial strains.
(86) Phase-Field Simulations.
(87) The domain structure was evolved by solving the time-dependent phase-field equations
(88)
where t is time, L is the kinetic coefficient related to the domain wall mobility and F is the total free energy, which is expressed by
(89)
where g is the gradient energy coefficient, x.sub.i is the spatial coordinate, and V is the system volume.
(90) In the x.sub.1 and x.sub.2 directions, periodic boundary conditions were assumed, whereas a superposition method was used along the x.sub.3 direction. For the constrained film, it was assumed that the top surface was stress-free, while the bottom interface was coherently clamped by the substrate. For the membrane, it was assumed that both the top surface and bottom interface were stress free. Equation (S3) was solved based on a semi-implicit Fourier-spectral method. The system size was 128x128x52x and the grid spacing was x=0.42 nm. Two types of strain conditions were applied to the VO.sub.2 films in the phase-field simulations.
(91) (1) Uniform Strain
11(x,y,z)=22(x,y,z)=0.0056(S5)
(2) Strain Gradient in Both the Out-Of-Plane and In-Plane Direction
(92)
(93) It was assumed that the interfacial energy between monoclinic and rutile phases was .sub.RM, and the interfacial energy between two monoclinic domains is .sub.MM.Math..sub.RM was not only structural interfacial energy, but also metal-insulator interfacial energy.sup.7,8, whereas .sub.MM refers to pure ferroelastic domain wall energy with the magnitude .sub.MM10 mJ m.sup.2. As a result, .sub.RM could be much larger than .sub.MM (i.e., interfacial energy ratio
(94)
making the effect of monoclinic domain boundaries negligible. To describe different monoclinic domains in the phase-field simulations, the phase-transition transformation strain .sub.ij.sup.00 was assumed to be position dependent, and the spatial distribution was fixed during the evolution of Equation S3. Note that .sub.ij.sup.00 in different positions was related by the rotation symmetry. The simulation setting was used to reflect the small interfacial energy ratio . The simulated domain evolution reflected experimental observations. It was experimentally confirmed that the phase transition dynamics was not much affected by the domain/grain.
(95) Stress Distribution Calculation.
(96) The stress distribution from the phase-field simulation was plotted and it was determined that the monoclinic domain walls have a large effect on the stress distribution. For single monoclinic domain, the stress was concentrated near the monoclinic-rutile phase boundaries. For multiple monoclinic domains, however, the stress was concentrated at both the monoclinic-rutile phase boundaries and domain wall-interface intersections.
(97) The mechanical boundary conditions were found to have a significant effect on the stress distribution. When both of the interfaces were subject to stress free boundary conditions, the local stress was largely reduced. For the coherently grown films, this could be well modeled by boundary conditions of the stress-free top surface and the constrained bottom interface (constrained bottom interface means that the displacement from the film to the substrate is continuous). For the incoherently grown films, the boundary conditions could be complex, and should be between the two limiting cases of the constrained film and the membranes. The simulation results showed that the mechanical boundary conditions of the incoherent interface played an important role in relieving the stress and preventing the formation of cracks during SPT.
(98) Electrical and Optical Measurements.
(99) Using the standard four-contact van der Pauw method with contacts of Al, the electrical resistivity was measured in vacuum as a function of temperature in VO.sub.2 films with or without SnO.sub.2 template. As a reference, the electrical transport was also measured for the fully coherent 8-nm-thick VO.sub.2 film on TiO.sub.2 substrate. It was quantitatively estimated that the sharpness of IMT for the SnO.sub.2-templated film was <1 K, by using the fill-width-at-half-maximum (FWHM) of the derivative curves. This sharpness is comparable with that of fully coherent 8-nm-thick VO.sub.2 films on bare TiO.sub.2, which is expected to show the sharpest MIT among VO.sub.2 films.
(100) Using spectroscopic ellipsometry, the refractive index n and extinction coefficient k were measured as a function of temperature. For the VO.sub.2 film on bare TiO.sub.2 substrate, the n exhibited gradual change across IMT. On the other hand, for the VO.sub.2 film on SnO.sub.2-templated TiO.sub.2, the n showed abrupt change for every across IMT.
(101) Fabrication and Characterizations of Optical Modulators.
(102) The Si-VO.sub.2 optical modulator was constructed on a VO.sub.2 layer 1410 with a thin transfer-printed single crystalline silicon layer 1410 (also referred to as a Si nanomembrane (NM)) (
(103) The word illustrative is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as illustrative is not necessarily to be construed as preferred or advantageous over other aspects or designs. Further, for the purposes of this disclosure and unless otherwise specified, a or an means one or more.
(104) The foregoing description of illustrative embodiments of the invention has been presented for purposes of illustration and of description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed, and modifications and variations are possible in light of the above teachings or may be acquired from practice of the invention. The embodiments were chosen and described in order to explain the principles of the invention and as practical applications of the invention to enable one skilled in the art to utilize the invention in various embodiments and with various modifications as suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims appended hereto and their equivalents.