Recent Progress on Piezotronic and Piezo‐Phototronic Effects in III‐Group Nitride Devices and Applications

Wurtzite‐structured III‐group nitrides, like GaN, InN, AlN, and their alloys, present both piezoelectric and semiconducting properties under straining owing to the polarization of ions in a crystal with non‐central symmetry. The piezoelectric polarization charges are created at the interface when a strain is applied. As a result, a piezoelectric potential (piezopotential) is produced, which is used as a “gate” to tune/control the charge transport behavior across a metal/semiconductor interface or a p‐n junction. This is called as piezotronic effect. A series of piezotronic devices and applications have been developed, such as piezotronic nanogenerators (NGs), piezotronic transistors, piezotronic logic devices, piezotronic electromechanical memories, piezotronic enhanced biochemical, and gas sensors and so on. With the flourished development of piezotronic effect, the piezo‐phototronic effect, as the three‐way coupling of piezoelectric polarization, semiconductor properties, and optical excitation, utilizes the piezopotential to modulate the energy band profile and control the carrier generation, transportation, separation, and/or recombination for improving performances of optoelectronic devices. This paper intends to provide an overview of the rapid progress in the emerging fields of piezotronics and piezo‐phototronics, covering from the fundamental principles to devices and applications. This study will provide important insight into the potential applications of GaN based electronic/optoelectronic devices in sensing, active flexible/stretchable electronics/optoelectronics, energy harvesting, human‐machine interfacing, biomedical diagnosis/therapy, and prosthetics.

     

Piezo‐Phototronic Matrix via a Nanowire Array

Piezoelectric semiconductors, such as ZnO and GaN, demonstrate multiproperty coupling effects toward various aspects of mechanical, electrical, and optical excitation. In particular, the three‐way coupling among semiconducting, photoexcitation, and piezoelectric characteristics in wurtzite‐structured semiconductors is established as a new field, which was first coined as piezo‐phototronics by Wang in 2010. The piezo‐phototronic effect can controllably modulate the charge‐carrier generation, separation, transport, and/or recombination in optical‐electronic processes by modifying the band structure at the metal–semiconductor or semiconductor–semiconductor heterojunction/interface. Here, the progress made in using the piezo‐phototronic effect for enhancing photodetectors, pressure sensors, light‐emitting diodes, and solar cells is reviewed. In comparison with previous works on a single piezoelectric semiconducting nanowire, piezo‐phototronic nanodevices built using nanowire arrays provide a promising platform for fabricating integrated optoelectronics with the realization of high‐spatial‐resolution imaging and fast responsivity.     

Enhanced Performance of a Self‐Powered Organic/Inorganic Photodetector by Pyro‐Phototronic and Piezo‐Phototronic Effects

Self‐powered photodetectors (PDs) have long been realized by utilizing photovoltaic effect and their performances can be effectively enhanced by introducing the piezo‐phototronic effect. Recently, a novel pyro‐phototronic effect is invented as an alternative approach for performance enhancement of self‐powered PDs. Here, a self‐powered organic/inorganic PD is demonstrated and the influences of externally applied strain on the pyro‐phototronic and the photovoltaic effects are thoroughly investigated. Under 325 nm 2.30 mW cm^‐2 UV illumination and at a ‐0.45% compressive strain, the PD's photocurrent is dramatically enhanced from ≈14.5 to ≈103 nA by combining the pyro‐phototronic and piezo‐phototronic effects together, showing a significant improvement of over 600%. Theoretical simulations have been carried out via the finite element method to propose the underlying working mechanism. Moreover, the pyro‐phototronic effect can be introduced by applying a ‐0.45% compressive strain to greatly enhance the PD's response to 442 nm illumination, including photocurrent, rise time, and fall time. This work provides in‐depth understandings about the pyro‐phototronic and the piezo‐phototronic effects on the performances of self‐powered PD to light sources with different wavelengths and indicates huge potential of these two effects in optoelectronic devices.     

Large‐Scale Horizontally Aligned ZnO Microrod Arrays with Controlled Orientation,Periodic Distribution as Building Blocks for Chip‐in Piezo‐Phototronic LEDs

A novel method of fabricating large‐scale horizontally aligned ZnO microrod arrays with controlled orientation and periodic distribution via combing technology is introduced. Horizontally aligned ZnO microrod arrays with uniform orientation and periodic distribution can be realized based on the conventional bottom‐up method prepared vertically aligned ZnO microrod matrix via the combing method. When the combing parameters are changed, the orientation of horizontally aligned ZnO microrod arrays can be adjusted (θ = 90° or 45°) in a plane and a misalignment angle of the microrods (0.3° to 2.3°) with low‐growth density can be obtained. To explore the potential applications based on the vertically and horizontally aligned ZnO microrods on p‐GaN layer, piezo‐phototronic devices such as heterojunction LEDs are built. Electroluminescence (EL) emission patterns can be adjusted for the vertically and horizontally aligned ZnO microrods/p‐GaN heterojunction LEDs by applying forward bias. Moreover, the emission color from UV‐blue to yellow‐green can be tuned by investigating the piezoelectric properties of the materials. The EL emission mechanisms of the LEDs are discussed in terms of band diagrams of the heterojunctions and carrier recombination processes.     

Electron Holographic Study of Semiconductor Light‐Emitting Diodes

Semiconductor light‐emitting diodes (LEDs), especially GaN‐based heterostructures, are widely used in light illumination. The lack of inversion symmetry of wurtzite crystal structures and the lattice mismatch at heterointerfaces cause large polarization fields with contributions from both spontaneous polarization and piezoelectric polarization, which in turn results in obvious quantum confined stark effect. It is possible to alleviate this effect if the local electrostatic fields and band alignment induced charge redistribution can be quantitatively determined across the heterostructures. In this Concept, the applications of electron holography to investigate semiconductor LEDs are summarized. Following the off‐axis electron holography scheme, the GaN‐based LED heterostructures including InGaN/GaN‐based quantum wells, other GaN‐based quantum wells, and other forms of GaN‐based LED materials are discussed, focusing on the local potential drops, polarization fields, and charge distributions. Moreover, GaAs‐based LED heterostructures are briefly discussed. The in‐line electron holography scheme emphasizes the capability of large area strain mapping across LED heterostructures with high spatial resolution and accuracy, which is combined with quantitative electrostatic measurements and other advanced transmission electron microscopy characterizations to provide an overall nanometer scale perspective of LED devices for further improvement in their electric and optical properties.     

Piezo‐Phototronic Effect on Selective Electron or Hole Transport through Depletion Region of Vis–NIR Broadband Photodiode

Silicon underpins nearly all microelectronics today and will continue to do so for some decades to come. However, for silicon photonics, the indirect band gap of silicon and lack of adjustability severely limit its use in applications such as broadband photodiodes. Here, a high‐performance p‐Si/n‐ZnO broadband photodiode working in a wide wavelength range from visible to near‐infrared light with high sensitivity, fast response, and good stability is reported. The absorption of near‐infrared wavelength light is significantly enhanced due to the nanostructured/textured top surface. The general performance of the broadband photodiodes can be further improved by the piezo‐phototronic effect. The enhancement of responsivity can reach a maximum of 78% to 442 nm illumination, the linearity and saturation limit to 1060 nm light are also significantly increased by applying external strains. The photodiode is illuminated with different wavelength lights to selectively choose the photogenerated charge carriers (either electrons or holes) passing through the depletion region, to investigate the piezo‐phototronic effect on electron or hole transport separately for the first time. This is essential for studying the basic principles in order to develop a full understanding about piezotronics and it also enables the development of the better performance of optoelectronics.     

Regulation of Charge Carrier Dynamics in ZnO Microarchitecture‐Based UV/Visible Photodetector via Photonic‐Strain Induced Effects

A feasible, morphological influence on photoresponse behavior of ZnO microarchitectures such as microwire (MW), coral‐like microstrip (CMS), fibril‐like clustered microwire (F‐MW) grown by one‐step carrier gas/metal catalyst “free” vapor transport technique is reported. Among them, ZnO F‐MW exhibits higher photocurrent (I_Ph) response, i.e., I_{Ph/ZnO F‐MW} > I_{Ph/ZnO CMS} > I_{Ph/ZnO MW}. The unique structural alignment of ZnO F‐MW has enhanced the I_Ph from 14.2 to 186, 221, 290 µA upon various light intensities such as 0 to 6, 11, 17 mW cm^?2 at λ_{405 nm}. Herein, the nature of the as‐fabricated ZnO photodetector (PD) is also demonstrated modulated by tuning the inner crystals piezoelectric potential through the piezo‐phototronic effect. The I_Ph response of PD decreases monotonically by introducing compressive strain along the length of the device, which is due to the synergistic effect between the induced piezoelectric polarization and photogenerated charge carriers across the metal–semiconductor interface. The current behavior observed at the two interfaces acting as the source (S) and drain (D) is carefully investigated by analyzing the Schottky barrier heights (Φ_SB). This work can pave the way for the development of geometrically modified strain induced performances of PD to promote next generation self‐powered optoelectronic integrated devices and switches.     

Correlative High‐Resolution Mapping of Strain and Charge Density in a Strained Piezoelectric Multilayer

A key to strain engineering of piezoelectric semiconductor devices is the quantitative assessment of the strain‐charge relationship. This is particularly demanding in current InGaN/GaN‐based light‐emitting diode (LED) designs as piezoelectric effects are known to degrade the device performance. Using the state‐of‐the‐art inline electron holography, we have obtained fully quantitative maps of the two‐dimensional strain tensor and total charge density in conventional blue LEDs and correlated these with sub‐nanometer spatial resolution. We show that the In_0.15Ga_0.85N quantum wells are compressively strained and elongated along the polar growth direction, exerting compressive stress/strain on the GaN quantum barriers. Interface sheet charges arising from a polarization gradient are obtained directly from the strain data and compared with the total charge density map, quantitatively verifying only 60% of the polarization charges are screened by electrons, leaving a substantial piezoelectric field in each In_0.15Ga_0.85N quantum well. The demonstrated capability of inline electron holography provides a technical breakthrough for future strain engineering of piezoelectric optoelectronic devices.     

Piezo‐Phototronic Effect Controlled Dual‐Channel Visible light Communication (PVLC) Using InGaN/GaN Multiquantum Well Nanopillars

Visible light communication (VLC) simultaneously provides illumination and communication via light emitting diodes (LEDs). Keeping a low bit error rate is essential to communication quality, and holding a stable brightness level is pivotal for illumination function. For the first time, a piezo‐phototronic effect controlled visible light communication (PVLC) system based on InGaN/GaN multiquantum wells nanopillars is demonstrated, in which the information is coded by mechanical straining. This approach of force coding is also instrumental to avoid LED blinks, which has less impact on illumination and is much safer to eyes than electrical on/off VLC. The two‐channel transmission mode of the system here shows great superiority in error self‐validation and error self‐elimination in comparison to VLC. This two‐channel PVLC system provides a suitable way to carry out noncontact, reliable communication under complex circumstances.     

Mixed Lead–Tin Halide Perovskites for Efficient and Wavelength‐Tunable Near‐Infrared Light‐Emitting Diodes

Near‐infrared (NIR) light‐emitting diodes (LEDs), with emission wavelengths between 800 and 950 nm, are useful for various applications, e.g., night‐vision devices, optical communication, and medical treatments. Yet, devices using thin film materials like organic semiconductors and lead based colloidal quantum dots face certain fundamental challenges that limit the improvement of external quantum efficiency (EQE), making the search of alternative NIR emitters important for the community. In this work, efficient NIR LEDs with tunable emission from 850 to 950 nm, using lead–tin (Pb‐Sn) halide perovskite as emitters are demonstrated. The best performing device exhibits an EQE of 5.0% with a peak emission wavelength of 917 nm, a turn‐on voltage of 1.65 V, and a radiance of 2.7 W Sr^?1 m^?2 when driven at 4.5 V. The emission spectra of mixed Pb‐Sn perovskites are tuned either by changing the Pb:Sn ratio or by incorporating bromide, and notably exhibit no phase separation during device operation. The work demonstrates that mixed Pb‐Sn perovskites are promising next generation NIR emitters.     

Surface‐Plasmon‐Enhanced Perovskite Light‐Emitting Diodes

Perovskite light‐emitting diodes (PeLEDs) have attracted considerable attention because of their potential in display and lighting applications. To promote commercialization of PeLEDs, it is important to improve the external quantum efficiency of the devices, which depends on their internal quantum efficiency (IQE) and light extraction efficiency. Optical simulations have revealed that 20–50% of the light generated in the device will be lost to surface plasmon (SP) modes formed in the metal/dielectric interfaces. Therefore, extracting the optical energy in SP modes to the air will greatly increase the light extraction efficiency of PeLEDs. In addition, the SPs can accelerate radiative recombination of the emitter via near‐field effects. Thus, the IQE of a PeLED can also be enhanced by SP manipulation. In this review, first, general concepts of the SPs and how they can enhance the efficiency of LEDs are introduced. Then recent progresses in SP‐enhanced emission of perovskite films and LEDs are systematically reviewed. After that, the challenges and opportunities of the SP‐enhanced PeLEDs are shown, followed by an outlook of further development of the SPs in perovskite optoelectronic devices.     

Efficient and Tunable Electroluminescence from In Situ Synthesized Perovskite Quantum Dots

Semiconductor quantum dots (QDs) are among the most promising next‐generation optoelectronic materials. QDs are generally obtained through either epitaxial or colloidal growth and carry the promise for solution‐processed high‐performance optoelectronic devices such as light‐emitting diodes (LEDs), solar cells, etc. Herein, a straightforward approach to synthesize perovskite QDs and demonstrate their applications in efficient LEDs is reported. The perovskite QDs with controllable crystal sizes and properties are in situ synthesized through one‐step spin‐coating from perovskite precursor solutions followed by thermal annealing. These perovskite QDs feature size‐dependent quantum confinement effect (with readily tunable emissions) and radiative monomolecular recombination. Despite the substantial structural inhomogeneity, the in situ generated perovskite QDs films emit narrow‐bandwidth emission and high color stability due to efficient energy transfer between nanostructures that sweeps away the unfavorable disorder effects. Based on these materials, efficient LEDs with external quantum efficiencies up to 11.0% are realized. This makes the technologically appealing in situ approach promising for further development of state‐of‐the‐art LED systems and other optoelectronic devices.     

Self‐Powered Si/CdS Flexible Photodetector with Broadband Response from 325 to 1550 nm Based on Pyro‐phototronic Effect: An Approach for Photosensing below Bandgap Energy

Cadmium sulfide (CdS) has received widespread attention as the building block of optoelectronic devices due to its extraordinary optoelectronic properties, low work function, and excellent thermal and chemical stability. Here, a self‐powered flexible photodetector (PD) based on p‐Si/n‐CdS nanowires heterostructure is fabricated. By introducing the pyro‐phototronic effect derived from wurtzite structured CdS, the self‐powered PD shows a broadband response range, even beyond the bandgap limitation, from UV (325 nm) to near infrared (1550 nm) under zero bias with fast response speed. The light‐induced pyroelectric potential is utilized to modulate the optoelectronic processes and thus improve the photoresponse performance. Lasers with different wavelengths have different effects on the self‐powered PDs and corresponding working mechanisms are carefully investigated. Upon 325 nm laser illumination, the rise time and fall time of the self‐powered PD are 245 and 277 µs, respectively, which are faster than those of most previously reported CdS‐based nanostructure PDs. Meanwhile, the photoresponsivity R and specific detectivity D* regarding to the relative peak‐to‐peak current are both enhanced by 67.8 times, compared with those only based on the photovoltaic effect‐induced photocurrent. The self‐powered flexible PD with fast speed, stable, and broadband response is expected to have extensive applications in various environments.     

Transient Light‐Emitting Diodes Constructed from Semiconductors and Transparent Conductors that Biodegrade Under Physiological Conditions

Transient forms of electronics, systems that disintegrate, dissolve, resorb, or sublime in a controlled manner after a well‐defined operating lifetime, are of interest for applications in hardware secure technologies, temporary biomedical implants, “green” consumer devices and other areas that cannot be addressed with conventional approaches. Broad sets of materials now exist for a range of transient electronic components, including transistors, diodes, antennas, sensors, and even batteries. This work reports the first examples of transient light‐emitting diodes (LEDs) that can completely dissolve in aqueous solutions to biologically and environmentally benign end products. Thin films of highly textured ZnO and polycrystalline Mo serve as semiconductors for light generation and conductors for transparent electrodes, respectively. The emitted light spans a range of visible wavelengths, where nanomembranes of monocrystalline silicon can serve as transient filters to yield red, green, and blue LEDs. Detailed characterization of the material chemistries and morphologies of the constituent layers, assessments of their performance properties, and studies of their dissolution processes define the underlying aspects. These results establish an electroluminescent light source technology for unique classes of optoelectronic systems that vanish into benign forms when exposed to aqueous conditions in the environment or in living organisms.     

CdS@SiO2 Core–Shell Electroluminescent Nanorod Arrays Based on a Metal–Insulator–Semiconductor Structure

Enormous advancement has been achieved in the field of one‐dimensional (1D) semiconductor light‐emitting devices (LEDs), however, LEDs based on 1D CdS nanostructures have been rarely reported. The fabrication of CdS@SiO₂ core–shell nanorod array LEDs based on a Au–SiO₂–CdS metal–insulator–semiconductor (MIS) structure is presented. The MIS LEDs exhibit strong yellow emission with a low threshold voltage of 2.7 V. Electroluminescence with a broad emission ranging from 450 nm to 800 nm and a shoulder peak at 700 nm is observed, which is related to the defects and surface states of the CdS nanorods. The influence of the SiO₂ shell thickness on the electroluminescence intensity is systematically investigated. The devices have a high light‐emitting spatial resolution of 1.5 μm and maintain an excellent emission property even after shelving at room temperature for at least three months. Moreover, the fabrication process is simple and cost effective and the MIS device could be fabricated on a flexible substrate, which holds great potential for application as a flexible light source. This prototype is expected to open up a new route towards the development of large‐scale light‐emitting devices with excellent attributes, such as high resolution, low cost, and good stability.     

Semiconductor Nanowire Light‐Emitting Diodes Grown on Metal: A Direction Toward Large‐Scale Fabrication of Nanowire Devices

Bottom‐up nanowires are attractive for realizing semiconductor devices with extreme heterostructures because strain relaxation through the nanowire sidewalls allows the combination of highly lattice mismatched materials without creating dislocations. The resulting nanowires are used to fabricate light‐emitting diodes (LEDs), lasers, solar cells, and sensors. However, expensive single crystalline substrates are commonly used as substrates for nanowire heterostructures as well as for epitaxial devices, which limits the manufacturability of nanowire devices. Here, nanowire LEDs directly grown and electrically integrated on metal are demonstrated. Optical and structural measurements reveal high‐quality, vertically aligned GaN nanowires on molybdenum and titanium films. Transmission electron microscopy confirms the composition variation in the polarization‐graded AlGaN nanowire LEDs. Blue to green electroluminescence is observed from InGaN quantum well active regions, while GaN active regions exhibit ultraviolet emission. These results demonstrate a pathway for large‐scale fabrication of solid state lighting and optoelectronics on metal foils or sheets.     

Room-Temperature Polarized Light-Emitting Diode-Based on a 2D Monolayer Semiconductor

Transition metal dichalcogenide (TMD)-based 2D monolayer semiconductors, with the direct bandgap and the large exciton binding energy, are widely studied to develop miniaturized optoelectronic devices, e.g., nanoscale light-emitting diodes (LEDs). However, in terms of polarization control, it is still quite challenging to realize polarized electroluminescence (EL) from TMD monolayers, especially at room temperature. Here, by using Ag nanowire top electrode, polarized LEDs are demonstrated based on 2D monolayer semiconductors (WSe₂, MoSe₂, and WS₂) at room temperature with a degree of polarization (DoP) ranging from 50% to 63%. The highly anisotropic EL emission comes from the 2D/Ag interface via the electron/hole injection and recombination process, where the EL emission is also enhanced by the polarization-dependent plasmonic resonance of the Ag nanowire. These findings introduce new insights into the design of polarized 2D LED devices at room temperature and may promote the development of miniaturized 2D optoelectronic devices.     

High‐Efficiency Single‐Component Organic Light‐Emitting Transistors

Construction of high‐performance organic light‐emitting transistors (OLETs) remains challenging due to the limited desired organic semiconductor materials. Here, two superior high mobility emissive organic semiconductors, 2,6‐diphenylanthracene (DPA) and 2,6‐di(2‐naphthyl) anthracene (dNaAnt), are introduced into the construction of OLETs. By optimizing the device geometry for balanced ambipolar efficient charge transport and using high‐quality DPA and dNaAnt single crystals as active layers, high‐efficiency single‐component OLETs are successfully fabricated, with the demonstration of strong and spatially controlled light emission within both p‐ and n‐ conducting channels and output of high external quantum efficiency (EQE). The obtained EQE values in current devices are approaching 1.61% for DPA‐OLETs and 1.75% for dNaAnt‐based OLETs, respectively, which are the highest EQE values for single‐component OLETs in the common device configuration reported so far. Moreover, high brightnesses of 1210 and 3180 cd m^?2 with current densities up to 1.3 and 8.4 kA cm^?2 are also achieved for DPA‐ and dNaAnt‐based OLETs, respectively. These results demonstrate the great potential applications of high mobility emissive organic semiconductors for next‐generation rapid development of high‐performance single‐component OLETs and their related organic integrated electro‐optical devices.     

Light‐Emitting Diodes with Cu‐Doped Colloidal Quantum Wells: From Ultrapure Green,Tunable Dual‐Emission to White Light

Copper‐doped colloidal quantum wells (Cu‐CQWs) are considered a new class of optoelectronic materials. To date, the electroluminescence (EL) property of Cu‐CQWs has not been revealed. Additionally, it is desirable to achieve ultrapure green, tunable dual‐emission and white light to satisfy the various requirement of display and lighting applications. Herein, light‐emitting diodes (LEDs) based on colloidal Cu‐CQWs are demonstrated. For the 0% Cu‐doped concentration, the LED exhibits Commission Internationale de L'Eclairage 1931 coordinates of (0.103, 0.797) with a narrow EL full‐wavelength at half‐maximum of 12 nm. For the 0.5% Cu‐doped concentration, a dual‐emission LED is realized. Remarkably, the dual emission can be tuned by manipulating the device engineering. Furthermore, at a high doping concentration of 2.4%, a white LED based on CQWs is developed. With the management of doping concentrations, the color tuning (green, dual‐emission to white) is shown. The findings not only show that LEDs with CQWs can exhibit polychromatic emission but also unlock a new direction to develop LEDs by exploiting 2D impurity‐doped CQWs that can be further extended to the application of other impurities (e.g., Mn, Ag).