Phase change materials in photonic devices

Cite as: J. Appl. Phys. 129, 030902 (2021); https://doi.org/10.1063/5.0027868

Submitted: 31 August 2020 . Accepted: 08 December 2020 . Published Online: 19 January 2021

Zilun Gong, Fuyi Yang, Letian Wang, Rui Chen, Junqiao Wu, Costas P. Grigoropoulos, and Jie Yao

COLLECTIONS

Paper published as part of the special topic on Phase-Change Materials: Syntheses, Fundamentals, and Applications

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Phase change materials in photonic devices

Cite as: J. Appl. Phys. 129, 030902 (2021); doi: 10.1063/5.0027868
Submitted: 31 August 2020 · Accepted: 8 December 2020 · View Online Export Citation CrossMark
Published Online: 19 January 2021

Zilun Gong,1 Fuyi Yang,1,2 Letian Wang,3 Rui Chen,1,2 Junqiao Wu,1,2 Costas P. Grigoropoulos,3
1,2,4,a)
and Jie Yao

AFFILIATIONS
1
Department of Materials Science and Engineering, University of California Berkeley, Berkeley, California 94720, USA
2
Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA
3
Laser Thermal Laboratory, Department of Mechanical Engineering, University of California, Berkeley, California 94720, USA
4
Tsinghua-Berkeley Shenzhen Institute, University of California, Berkeley, California 94720, USA

Note: This paper is part of the Special Topic on Phase-Change Materials: Syntheses, Fundamentals, and Applications.
a)
Author to whom correspondence should be addressed: yaojie@berkeley.edu

ABSTRACT
Recent developments in reconfigurable photonic devices highly rely on the effective refractive index change enabled by phase change materi-
als (PCMs) as either dielectric surroundings or constituting materials. This universal characteristic, tunable refractive index, is shared among
various kinds of PCMs and has been successfully utilized to achieve multilevel modulations for both free-space and integrated photonics.
In this Perspective, we briefly recapitulate the fundamental mechanisms of phase transitions for three dominant PCMs. The progress in
integrating different PCMs with on-chip silicon photonics and periodic antenna arrays are reviewed and analyzed in parallel. We also
discuss the existing problems of PCM photonics, for example, the compatibility with commercial production line, the stability issue, and
accessibility of the stimuli. In the end, we provide the outlook for the improving material engineering of PCM and multi-functional
PCM-based photonics devices.

Published under license by AIP Publishing. https://doi.org/10.1063/5.0027868

I. INTRODUCTION electronic structure of the material, hence modulating the refractive

index. Those materials with multiple stable structural and elec-
In the interactions of light with matter, discrete electric
charges in a matter are driven into oscillation by incident electro- tronic states are called phase-change materials (PCMs).2 More
magnetic waves. Secondary radiations or scattered radiations are practically, the phase of the PCMs can be controlled by parameters
emitted from these accelerated charges. Each charge responses not including temperature, electric current, strain, etc., which enables
only to the incident field but also to the secondary field generated more flexible routes toward dynamic control of refractive indices.
by neighboring charges in solid-state materials. The reflection and The possibility of the significant change in refractive indexes brings
refraction are, therefore, the superposition of secondary radiations more degree of freedom in designing multifunctional and dynamic
from coupled charges. Refractive index, which depends on charge devices for both free space modulation and photonic integrated cir-
density and the polarizability of a charge, is introduced to describe cuits (PICs).
the overall scattering phenomena macroscopically. Optical devices, PCMs typically undergo structural changes at phase transition
which guide and manipulate electromagnetic wave based on diffrac- temperatures, which result in drastic changes in the electronic
tion and reflection, thus highly rely on the success in controlling of structure and refractive indices.1,2 For example, pronounced change
the refractive indices of constituting materials. of electric polarizability, hence the resultant refractive index, is
Increasing demand for better control of light propagation has expected when some PCMs are transitioning from amorphous to
led to extensive explorations on refractive index engineering. For crystalline states accompanied by the reconfiguration of chemical
example, different types of metamaterials have been designed to bonds. One can use this optical contrast in photonic devices to
introduce sub-wavelength structures that tune the effective refrac- realize various functionalities. For example, the chalcogenide mate-
tive index, usually through resonances of artificial “atoms.” In con- rial family is successful in the applications of digital versatile disk
trast to the metamaterials, one can also change the underlying random access memory (DVD-RAM) and Blue-ray disks.3 The

J. Appl. Phys. 129, 030902 (2021); doi: 10.1063/5.0027868 129, 030902-1

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high-power laser is used to induce local phase transition by heat transition (MIT) accompanied by large refractive index change. The
treatment (writing data), and then the low-power laser is used to second category is the germanium–antimony–telluride (GST) family
measure the reflectance of the material (reading data). More with fast crystalline-amorphous phase transition.3 Thanks to the res-
recently, researchers have integrated the PCMs into novel plat- onance bonds in the metastable crystalline phase, giant optical con-
forms, such as metasurface,4–6 color printing,7–9 and integrated trast is available, which is uncommon for semiconductor materials.
modulators,10–12 which pave the road toward broader applications The third category is silicon (Si), whose (stable) crystalline FCC
of PCMs. phase and amorphous phase show meaningful contrast in the visible
In this Perspective, we will review three categories of PCMs and frequency range.13 The wide applications of silicon, especially in
their application in optical devices and discuss their potential devel- photonics, make this relatively young direction highly attractive. We
opments in the future. The first category is correlated materials that will discuss some recent advances of controlling the phase change of
are subject to Mott phase transition.1 The vanadium oxide family, silicon via a pulsed laser.14,15 In the meantime, we will also provide
especially the vanadium dioxide (VO2), shows metal–insulator some thoughts on the future research directions of those three

FIG. 1. VO2 modulation in integrated photonics. (a) Schematic and SEM image of the VO2 modulator. 2 μm-long polycrystalline VO2 tab is deposited on the ring resona-
tor.21 (b) Illustration of a phase-change absorber where MIT induces a broadband change in absorption Δα.22 (c) Schematic of electron-absorption VO2-Si modulator with
TM to TE conversion.23 (a) Reproduced with permission from Briggs et al., Opt. Express 18, 11192 (2010). Copyright 2010, Optical Society of America. (b) Reproduced
with permission from Ryckman et al., Opt. Express 21, 10753 (2013). Copyright 2013, Optical Society of America. (c) Reproduced with permission from Diana et al.,
J. Opt. 19 (2017). Copyright 2017, IOP Publishing Ltd.

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categories. We hope these discussions can trigger more extensive its insulating phase, these vanadium atoms pair along the c axis
explorations of PCMs in photonic applications. with a slight twist, which leads to a monoclinic structure.
Therefore, we shall refer to the two phases as R and M1, respec-
tively. In addition, VO2 has another monoclinic phase M2 when
II. VO2 tensile strain is applied along the c axis. The phase diagram has
Vanadium oxides are a material family known for their also been developed.20 In most circumstances, the insulating phase
strong-correlation behaviors.16 Typical band structure theory is of VO2 devices is predominantly M1 phase.
based on the single-electron approximation, where the Coulomb Multiple factors make VO2 a good candidate for tunable
interactions between electrons are omitted. However, in the strong- optical devices. First, as mentioned above, the phase transition pro-
correlation materials, the electron–electron interactions give rise to vides a large optical contrast as a function of temperature. To be
rich physics, such as Mott insulators. Mott insulators should specific, the M1 phase has low loss (transparent), while the R phase
conduct electricity under conventional band theories but show a is very absorbing (reflective) at near to mid-infrared range.19 For
temperature-dependent conductivity: they are insulators at low- example, a silicon waveguide partly covered by VO2 film forms an
temperature phase and conductors at high-temperature phase. This optical switch upon MIT. At high temperature, when VO2 is in the
metal–insulator transition (MIT) is usually referred to as “Mott R phase and becomes very lossy, the electromagnetic field in the
transition.”17 Vanadium dioxide, or VO2, is a typical Mott insulator waveguide will be largely absorbed by the R phase and the trans-
that has a phase transition temperature quite close to room temper- mission is annihilated. This idea is compatible with existing PIC
ature, at around 68 °C, making it one of the most interesting PCMs devices, such as ring resonators21,22 [Figs. 1(a) and 1(b)] and polar-
that have been explored. Applying compressive strain or doping the ization converters23 [Fig. 1(c)]. Compact optical switches were
material with tungsten (W) can further bring down the MIT tem- demonstrated using the silicon-on-insulator platforms. In addition
perature.18 Accompanied with the phase transition is a large optical to the optical waveguide, the plasmonic waveguide can also take
contrast: the relative dielectric constant is −35 + 199i for the metal- advantage of VO2 with metallic structures.24
lic phase and 4.9 for the insulating phase around 10.6 μm.1,19 VO2 is also capable of modulating the electromagnetic
In its metallic phase, VO2 has a rutile-type structure with wave by changing the optical modes in a periodic structure. A one-
vanadium atoms equally spaced along the corresponding c axis. In dimensional solid-state tunable Bragg filter using a VO2 film

FIG. 2. VO2 modulating free-space light with periodic structures. (a) Schematic of a tunable Bragg filter with VO2 thin film.25 (b) Schematic, optical, and SEM images of
mid-infrared antenna array with a 250 nm thick VO2 layer and a top interdigitated metal strip array.26 (c) Schematic of hybrid split-ring resonator (SRR) metamaterials
based on vanadium oxide.30 These designs yield multiple resonances in the near-IR spectrum. As the temperature is increased above the insulator-metal transition temper-
ature of VO2, the near-IR spectral reflection properties of the SRR array become similar to those of the non-patterned metal phase VO2 film. (d) Memory-oxide hybrid-
metamaterial device with gold SRR array lithographically fabricated on VO2 film.28 Simultaneous dc-transport and far-infrared probing of the metamaterial demonstrate that
as VO2 passes through its insulator-to-metal transition, resistance drops and the SRR resonance frequency decreases. (a) Reproduced with permission from Wang et al.,
Opt. Express 24, 20365 (2016). Copyright 2016, Optical Society of America. (b) Reproduced with permission from Li et al., J. Mod. Opt. 65, 1809 (2018). Copyright 2018,
Informa UK Limited, trading as Taylor & Francis Group. (c) Reproduced with permission from Dicken et al., Opt. Express 17, 18330 (2009). Copyright 2009, Optical
Society of America. (d) Reproduced with permission from Driscoll et al., Science 325, 1518 (2009). Copyright 2013, Optical Society of America.

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sandwiched between two Bragg reflectors has been demonstrated25 [Figs. 3(a) and 3(b)]. Besides, the process is repeatable, meaning
[Fig. 2(a)]. The transparency window of the filter can be readily that patterns can be erased by global heating. Another approach for
tuned by global heating. An electrically tunable metallic grating can local phase control is to induce local defects from ion radiation38 as
be achieved by adding a layer of VO2 film underneath it26 shown in Fig. 3(c). The effect is similar to the local doping of W
[Fig. 2(b)]. For two-dimensional devices, VO2 films are usually atoms, that the MIT temperature is lowered by knock off V atoms
paired with an array of metallic optical antennas.27,28 The antennas in the lattice. Within proper ambient temperature range, the
form a 2D photonic crystal29 or function as a metasurface, while devices show optical patterns defined by ion radiation [Fig. 3(d)].
the MIT of VO2 affects or simply shifts the optical mode of these Third, significant change in the VO2 crystal lattice, thus the
antennas30–33 [Figs. 2(c) and 2(d)]. It is also feasible to directly strain, is induced during the phase transition, which poses opportu-
pattern antennas on VO2 using lithography34 or bottom-up synthe- nities for optomechanical devices. Benefiting from the strain across
sis,35 but the finite granular feature of VO2 makes it challenging to the phase transition, VO2-based micro-actuators are able to show
fabricate nanostructures with high precision. giant normalized actuation amplitude with high output39
Second, although the single-crystalline VO2 has very little hys- [Fig. 4(a)]. Micro-cantilevers with VO2 layer is known for good
teresis around 1 °C in the phase transition, the deposited multi- mechanical response as a function of heating40,41 [Fig. 4(b)]. Our
crystalline thin film can show hysteresis with width above 10 °C. group demonstrated a tunable infrared grating that the metallic
Studies have shown a correlation between the hysteresis width and grating is flat and curved when VO2 is in metallic and insulating
grain disorientations.36 A broad hysteresis makes VO2 promising phases, respectively42 [Fig. 4(c)]. Therefore, the reflection is modu-
for optical storage and local phase manipulations because the same lated. Note that such devices rely on the mechanical rather than
ambient temperature can host two states depending on the heat optical properties of VO2 MIT to function.
treatment.28 For example, one can control the ambient temperature The phase transition temperature of VO2 is relatively low and
within the hysteresis loop and then use the laser-writing technique can be further lowered to room temperature with appropriate
to raise the local temperature outside the hysteresis. As a doping. Therefore, the high-temperature VO2 R phase can be
consequence, the local optical contrast is obtained even after accessed thermally, electrically, or with ultrafast optical pulses. Due
the local point cools down to ambient temperature. In this way, to the volatile nature of VO2 transition, transient optical modulated
we can “write” antennas and metasurfaces on a VO2 film photonic applications are supported by the VO2 system. When
and “read” the information using low-power mid-infrared light37 thermal heating serves as the stimulus, VO2 photonic devices have

FIG. 3. Local phase manipulation of VO2 film. (a) Schematic of laser writing different photonic operator patterns on a metacanvas37 and temperature-dependent resistance
of VO2 film where the transition temperature is denoted by a vertical dashed line. (b) Optical image of a hologram compiled on the metacanvas consisting of the informa-
tion of two-spot image with 18 beam steering phase distribution. Target two-spot images, corresponding phase distribution, and experimental holographic images are
shown from (i) to (vi).37 (c) Spatially selective defect engineering achieved by ion beam irradiation through a mask.38 (d) Temperature-dependent transmittance of a 100 nm
VO2 film irradiated with Ar+ for various ion fluences. Contrast between the insulating and metallic phases of VO2 is highest at intermediate temperature (
60 ).38 (a) and
(b) Reproduced with permission from Dong et al., Adv. Mater. 30, 1703878 (2018). Copyright 2017, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (c) and (d)
Reproduced with permission from Rensberg et al., Nano Lett. 16, 1050 (2016). Copyright 2015, American Chemical Society.

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FIG. 4. VO2 in opto-mechanical devices. (a) A VO2 cantilevered microactuator showing a large bending amplitude when temperature is changing.39 (b) VO2 trilayer cantile-
ver actuator design and SEM image of a released device. Temperature-dependent resistivity and cantilever deflection are also shown.40 (c) Schematics of
microelectron-opto-mechanical device with curved cantilevers at room temperature and flat cantilevers at temperature above Tc.42 (a) Reproduced with permission from Liu
et al., Nano Lett. 12, 6302 (2012). Copyright 2012, American Chemical Society. (b) Reproduced with permission from Dong et al., Appl. Phys. Lett. 109 (2016). Copyright
2016, AIP publishing LLC. (c) Reproduced with permission from Wang et al., Nano Lett. 18, 1637 (2018). Copyright 2018, American Chemical Society.

high extinction ratio and low loss, though the switching speed is because the data are accessed by the laser. The materials in the
inherently slow, on the order of seconds or minutes.43 On the other GST family typically have two stable phases at room temperature:
hand, electric and optical pulses enable relatively faster switching the amorphous phase and the metastable crystalline (rock salt-type)
speed around 2 ns.43 phase. One can use different heat treatment to induce phase transi-
A major challenge of implementing VO2 in a practical device tions in both ways: heating the material followed by quenching
is its stability. A VO2 film would quickly oxidize to V2O5 when results in amorphous phase; while maintaining the temperature
exposed to air so that the devices with VO2 film usually suffer from above the glass transition temperature for long enough time results
limited lifetime. A common way to resolve this problem is by utiliz- in a crystallization phase.47 Therefore, both phases can be manipu-
ing protective layers to keep VO2 from oxidation and deterioration. lated and read via a focused laser, which makes the GST family
Researchers have used cladding materials to sandwich VO2 to make ideal for data storage. Furthermore, it is possible to take advantage
a stable smart window.45 Hydrophobic and hafnium dioxide layers of the tunable refractive index and design optical devices.2,48
have also been developed recently for encapsulation purposes, It is generally agreed in the literature that such phase transi-
which show improved stability.44 Successful tackling of the oxida- tions in GST do not require the breaking of the chemical bond,
tion problem of VO2 and reduction of production cost by low- which explains the fast transition speed.47 At metastable rock salt
temperature deposition methods are necessary steps toward the phase, the Te atoms occupy one face-centered-cubic (FCC) lattice,
commercial application of VO2-based smart windows and tunable while the Ga atoms, Sb atoms, and vacancies occupy the other FCC
metamaterials for long-term use. sublattice. For example, in Ge2As2Te5, Ge and Sb atoms occupy
40% of the other FCC sublattice, respectively, while the remaining
20% sites are vacancies.49 In the metastable phase, there are reso-
III. GST nance bonds between short and long (nearest neighbor and next-
The family of chalcogenides hosts a variety of PCMs. nearest neighbor) Te–Ge bonds,50 which explain the large index
Specifically, most phase change materials are found within the contrast (the metastable phase is more reflective than the amor-
ternary Ge–Sb–Te (GST) phase diagram.46 The pseudo-binary line phous phase). Upon excitation, the resonance bonds undergo
between GeTe and Sb2Te3 is home to some of the most successful Peierls distortion.51 The Ge atom changes from the center of a Te
PCM products on the market, including the DVD-RAM and octahedral to the center of a Te tetrahedral.47,52 Once distortion
Blue-ray disk.3 occurs, it triggers the collapse of long-range order and therefore the
A candidate material for non-volatile data storage must have phase transition.47,51
two stable phases representing two distinct states with a fast transi- Implementing the GST in the tunable optical devices serves a
tion. Besides, the two phases should have large optical contrast similar role as VO2. Because both phases are stable in a wide

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temperature range (including room temperature), GST has long solution to the dynamic metasurface that the communities have
been applied as a platform with excellent non-volatility. Here, we been longing for. Both wire (bar) antennas62,63 and split-ring
review some of the device demonstrations using GST, specifically antennas63–65 covered by the GST film show reversible and effective
Ge2Sb2Te5 because of its low loss in the near-infrared range. For optical switching behavior as shown in Fig. 6(c). Another approach
detailed discussions of metal-chalcogenide-metal (MCM) trilayered is to use lithography techniques to directly fabricate antennas on
nanostructures, their design methodology, and potential challenges, the GST film without metallic structures. The one-dimensional and
there was already a very good review paper;46 here, we mainly focus two-dimensional metasurfaces made of GST both have been
on how the GST interacts with electromagnetic waves in various proposed.6,66,67
photonic systems. First, GST can be used to affect the mode in the Third, local manipulation of phase is also feasible thanks to
plasmonic or optical waveguides. For example, a switch is achieved the laser writing and near-field probe techniques. Starting from a
when GST is applied on the waveguide or ring resonators53–55 homogeneous GST film, focused laser can create an arbitrary
[Figs. 5(a) and 5(b)]. The transmission characteristics are modu- pattern by induction local phase transition5,68 [Fig. 7(a)]. The pixel
lated upon phase transition. Furthermore, researchers demonstrated size of the pattern is determined by the focal point of laser.
all-optically controlled memory: high power laser is used to write Sub-0.6-μm pixel size was demonstrated by a femtosecond laser.5
the data by heating up the GST, while the low power laser is used This technique also gave rise to surface phonon polariton study by
to read the data by measuring transmission56 [Fig. 5(c)]. It is creating a resonance chamber on a smooth GST film.68
similar to the familiar flash memory that high and low voltages are To further push down the spatial resolution, color printing
used to write and read data, respectively. Phonon polariton-based was demonstrated using an atomic force microscope (AFM)7,8
rewritable waveguides and refractive optical elements such as [Fig. 7(b)]. The basic principle is to pass current locally through
metalenses have also been demonstrated by controlling the the GST film, and Joule heating induces phase transition. It is note-
surrounding dielectric environment comprising the low-loss phase worthy that all the applications discussed except for color printing
change GST.57 are binary: the optical memory and switches all have two states,
Second, the GST can modulate the interaction of an electro- whichever the forms are (waveguide, metasurface, etc.). However,
magnetic wave with periodic structures. Most common demonstra- in the more recent demonstration of color printing, gray scale was
tions are using GST films with metallic antennas. Tunable achieved. It means that one can control the percentage of phase
absorbers with large filling ratio metallic structures58–60 or tunable transition locally.8
photonic crystal showing Fano resonances61 can be made based on Accompanied with bond reconfiguration during phase transi-
this concept [Figs. 6(a) and 6(b)]. In addition, GST became a tion in GST, optical loss increases significantly due to free carrier

FIG. 5. GST modulation in integrated photonics. (a) An optical switch with two microrings coupled to a waveguide. One of the silicon resonators is overcladded by GST.54
(b) Plasmonic waveguide with a GST strip in the middle. The intensity at the out-coupling grating changes strongly upon change in the GST phase, leading to a strong dif-
ferential signal.53 (c) An all-optical on-chip memory device with GST section on the top of the nanophotonic waveguide.55 Less optical power is transmitted through the
waveguide if the GST is in the crystalline state (level 0) than when it is in the amorphous state (level 1). TE optical mode in the waveguide evanescently couples to amor-
phous GST. (a) Reproduced with permission from Rudé et al., Appl. Phys. Lett. 103, 141119 (2013). Copyright 2013, AIP Publishing LLC. (b) Reproduced with permission
from Rudé et al., ACS Photonics 2, 669 (2015). Copyright 2015, American Chemical Society. (c) Reproduced with permission from Ríos et al., Nat. Photonics 9, 725
(2015). Copyright 2016, Springer Nature.

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absorption limiting their potential usage in the short wavelength optical switching, metasurface color displays, tunable perfect absorber,
range. Successful breaking of the concurrent index and loss and performance enhancement of existing plasmonic devices.74,76–78
changes based on compositionally optimized alloy Ge–Sb–Se–Te Looking forward to further applications of GST in photonic
(GSST) has been shown to alleviate the loss problem by only trig- devices, we believe the partial phase transition8 is promising in
gering the refractive index changes without introducing loss bringing more degree of freedom into the control. In addition,
penalty during phase transition.69 Based on this optimized material existing local phase control relies on pixel-by-pixel tuning, which is
platform, low-loss reflective pixe,69 reconfigurable metasurface,70 very slow. With the help of masks, it is possible to expose the
varifocal metalens,71 integrated reversible crossbar switching,72 and whole film and speed up the formation of a pattern.
on-chip photonic multilevel memory73 have been demonstrated From manufacturability and quality control aspects, the chal-
with enhanced performances. cogenide alloys are not compatible with conventional etching and
To further push the working frequency to the UV-visible cleaning processes. Improved methods including chemical vapor
spectral range (200–500 nm), tunable plasmonic responses of nano- deposition (CVD) and atomic layer deposition (ALD) techniques
structured GST are exploited.74 The plasmon resonance due to the are often time-consuming and expensive. However, the develop-
negative permittivity of GST in the short-wavelength range can be ments in physical vapor deposition (PVD) and new recipes for dry
also considered as a design parameter for tuning the PCM-based etching and cleaning processes have paved the way for integrated
optical devices.75 Controllable functionalities in the UV-visible range GST photonic application.79,80 Several proof-of-concept demonstra-
that cannot be achieved using conventional plasmonic metals such as tions of the active GST photonic devices have been prepared on the

FIG. 6. GST modulating free-space light with periodic structures. (a) A switchable absorber utilizing the amorphous-to-crystalline phase transition in GST.58 (b) Simulated
transmission spectra of GST-Au hybrid plasmonic crystals with the GST layer in amorphous and crystalline phases, and a plasmonic crystal without underneath GST.61 (c)
An all-optical, non-volatile, chalcogenide glass metamaterial switch that provides for high contrast transmission and reflection switching of signals at wavelengths close to
the metamaterial resonances. A single laser pulse converts a chalcogenide phase-change nanolayer back and forth between amorphous and crystalline states.65 (a)
Reproduced with permission from Tittl et al., Adv. Mater. 27, 4597 (2015). Copyright 2015, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (b) Reproduced with permis-
sion from Chen et al., Opt. Express 21, 13691 (2013). Copyright 2013, Optical Society of America. (c) Reproduced with permission from Gholipour et al., Adv. Mater. 25,
3050 (2013). Copyright 2013, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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FIG. 7. Local phase manipulation on the GST film. (a) Schematic of writing reconfigurable photonic devices in GST. Optical excitation changes the complex refractive
index of the film by converting continuously from the amorphous to crystalline state, allowing films with complex refractive index profiles to be written.5 Optical images of
the lens patterns in the GST film with transverse chromatic aberration and corrected chromatic aberration are shown. (b) Grayscale images rendering and employing the
GST film.8 (a) Reproduced with permission from Wang et al., Nat. Photonics 10, 60 (2016). Copyright 2015, Springer Nature. (b) Reproduced with permission from Ríos
et al., Adv. Mater. 28, 4720 (2016). Copyright 2016, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

CMOS compatible silicon wafer using an established method been well studied on thin film88 and nanostructures.89 The transi-
showing expected switching behavior with short switching ent melting will incur minimum thermal damage to the substrate.
time.69,81,82 Along with the progresses of compound PCMs, Excimer laser annealing (ELA) has been the workhorse for the
monoatomic phase change materials without requirement of main- display TFT manufacturing for over a decade. The local melting is
taining stoichiometry during growth have also been proposed.13–15 followed by slower cooling and crystallization driven by the heat
diffusion to the substrate. On the other hand, if cooling is fast,
pulsed laser-induced amorphization will happen on bulk materi-
IV. Si als14 and thin films.15 Studies have shown that the timescale of
Silicon (Si), the ubiquitous material for the semiconductor laser-induced silicon phase transformation varies from tens of
industry and emerging photonics industry,83 presents attractive fea- nanoseconds88 to sub-nanosecond 90 and, therefore, is of similar
tures as a phase change material. From the optical performance order of magnitude to current phase change materials. Hence,
point of view, it features high refractive index and relatively low pulsed laser irradiation is a promising route for reversible phase
loss in the visible wavelength range, especially the NUV range.84 Si change in silicon nanodomains.
maintains consistent chemical composition upon repeated optical Researchers recently showed that the nanosecond pulsed laser
modulation. Both crystalline and amorphous resonators have been could effectively amorphize polycrystalline silicon nanoresonators
widely applied in many metasurfaces and integrated photonic of 120–300 nm in diameter.91 The difference in the crystalline and
devices.84–87 If the phase transformation and associated refractive amorphous silicon’s refractive indices was manifested in the switch-
index change of silicon itself can be utilized, the active integrated ing of Mie resonances. A later report13 confirmed that polycrystal-
photonic device can then be readily achieved with eliminated depo- line and amorphous phase silicon resonators could be reversibly
sition and etching steps to lower the cost and increase the yield. transformed within nanoseconds [Figs. 8(a)–8(d)]. Nanosecond
Crystallinity of silicon can be easily controlled through manip- laser pulses of different energies were used to transform the nano-
ulating the temperature of low-pressure chemical vapor deposition domains with sizes down to 200 nm. These processes offered 20%
(LPCVD). Silicon’s melting point could be perceived a barrier for non-volatile reflectance modulation, which could be repeated over
crystallinity control; but, in fact, pulsed laser crystallization has 400 times. As no significant deformation was observed, the

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FIG. 8. Concept and application of reversible phase transformation of silicon nanostructures.13 (a) Schematics of reversible phase transformations of silicon nanodisks.
Through laser melting the a-Si transformed to liquid and upon solidification, the material transformed to c-Si. (b) Nanosecond laser parameters used for fast reversible
phase transformations of a single nanodisk. (c) Transmission spectra of pristine a-Si disks, the crystallized nanodisk, and reamorphized nanodisk with 215 nm in diameter.
(d) The concept of pixel-addressable rewritable visible metasurfaces for display and optical wavefront control. (a)–(d) Reproduced with permission from Wang et al., Adv.
Funct. Mater. 1910784, 1 (2020). Copyright 2020, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

resonance could be preserved, paving the way for reversible switch- improved. Along with the mature material growth capability and
ing of photonic devices. By incorporating high N.A. laser writing,92 compatibility with CMOS technique, GST and silicon are more pre-
this work demonstrated a proof-of-concept experiment for dielec- ferred for non-volatile integrated photonic applications.
tric display and visible wavefront control. Besides the on-demand
writing, optical switching will greatly expand the device functionali-
ties of silicon-based nanophotonics.87 Typical applications include V. Summary
turning on and off Fano resonances93 and edge states,94 modifying Refractive index change enabled by PCMs has been utilized to
demultiplexer functionalities,95 and offering multilevel tunability to achieve switching in integrated photonics, modulation of electro-
hybrid metamaterials.96 magnetic modes in periodic structures, and manipulation of local
For GST and silicon with high melting temperature, in order optical contrast. Concept demonstrations show the potential of
to overcome the energy barrier of the amorphous-crystalline struc- their practical applications. However, the problems associated with
ture, electrical and optical pulses are needed to trigger the transi- the integration of the PCMs with commercial production line, the
tion. Free-space propagating optical pulses have been widely used stability over time, and accessibility of the stimuli for phase transi-
to demonstrate GST or silicon-based tunable photonic devices. tion point out the direction of research in future. The independent
However, these devices and setups suffer from the large footprints control of local phases will definitely bring more degree of freedom
and only suitable for free-space light modulation applications. The and advance the design of multi-functional devices. Better under-
possibility to integrate both pump and probe optical pulses on standing and further material engineering such as doping or alloy-
chip, switching speed, and energy consumption will be further ing will not only lower the transition temperature, but also allow

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30
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