Materials can be transformed from one crystalline phase to another by using an electric field to control ion transfer, in a process that can be harnessed in applications such as batteries, smart windows and fuel cells. Increasing the number of transferrable ion species and of accessible crystalline phases could in principle greatly enrich material functionality. However, studies have so far focused mainly on the evolution and control of single ionic species (for example, oxygen, hydrogen or lithium ions). Here we describe the reversible and non-volatile electric-field control of dual-ion (oxygen and hydrogen) phase transformations, with associated electrochromic and magnetoelectric effects. We show that controlling the insertion and extraction of oxygen and hydrogen ions independently of each other can direct reversible phase transformations among three different material phases: the perovskite SrCoO (ref. 12), the brownmillerite SrCoO (ref. 13), and a hitherto-unexplored phase, HSrCoO. By analysing the distinct optical absorption properties of these phases, we demonstrate selective manipulation of spectral transparency in the visible-light and infrared regions, revealing a dual-band electrochromic effect that could see application in smart windows. Moreover, the starkly different magnetic and electric properties of the three phases-HSrCoO is a weakly ferromagnetic insulator, SrCoO is a ferromagnetic metal, and SrCoO is an antiferromagnetic insulator-enable an unusual form of magnetoelectric coupling, allowing electric-field control of three different magnetic ground states. These findings open up opportunities for the electric-field control of multistate phase transformations with rich functionalities.

Ionic substitution forms an essential pathway to manipulate the structural phase, carrier density and crystalline symmetry of materials via ion-electron-lattice coupling, leading to a rich spectrum of electronic states in strongly correlated systems. Using the ferromagnetic metal SrRuO 3 as a model system, we demonstrate an efficient and reversible control of both structural and electronic phase transformations through the electric-field controlled proton evolution with ionic liquid gating. The insertion of protons results in a large structural expansion and increased carrier density, leading to an exotic ferromagnetic to paramagnetic phase transition. Importantly, we reveal a novel protonated compound of HSrRuO 3 with paramagnetic metallic as ground state. We observe a topological Hall effect at the boundary of the phase transition due to the proton concentration gradient across the film-depth. We envision that electric-field controlled protonation opens up a pathway to explore novel electronic states and material functionalities in protonated material systems.

Field-effect transistors with ionic-liquid gating (ILG) have been widely employed and have led to numerous intriguing phenomena in the last decade, due to the associated excellent carrier-density tunability. However, the role of the electrochemical effect during ILG has become a heavily debated topic recently. Herein, using ILG, a field-induced insulator-to-metal transition is achieved in WO thin films with the emergence of structural transformations of the whole films. The subsequent secondary-ion mass spectrometry study provides solid evidence that electrochemically driven hydrogen evolution dominates the discovered electrical and structural transformation through surface absorption and bulk intercalation.

Electric-field-driven oxygen ion evolution in the metal/oxide heterostructures emerges as an effective approach to achieve the electric-field control of ferromagnetism. However, the involved redox reaction of the metal layer typically requires extended operation time and elevated temperature condition, which greatly hinders its practical applications. Here, we achieve reversible sub-millisecond and room-temperature electric-field control of ferromagnetism in the Co layer of a Co/SrCoO2.5 system accompanied by bipolar resistance switching. In contrast to the previously reported redox reaction scenario, the oxygen ion evolution occurs only within the SrCoO2.5 layer, which serves as an oxygen ion gating layer, leading to modulation of the interfacial oxygen stoichiometry and magnetic state. This work identifies a simple and effective pathway to realize the electric-field control of ferromagnetism at room temperature, and may lead to applications that take advantage of both the resistance switching and magnetoelectric coupling.

Ionic evolution–induced phase transformation can lead to wide ranges of novel material functionalities with promising applications. Here, using the gating voltage during ionic liquid gating as a tuning knob, the brownmillerite SrCoO2.5 is transformed into a series of protonated HxSrCoO2.5 phases with distinct hydrogen contents. The unexpected electron to charge‐neutral doping crossover along with the increase of proton concentration from x = 1 to 2 suggests the formation of exotic charge neutral H–H dimers for higher proton concentration, which is directly visualized at the vacant tetrahedron by scanning transmission electron microscopy and then further supported by first principles calculations. Although the H–H dimers cause no change of the valency of Co2+ ions, they result in clear enhancement of electronic bandgap and suppression of magnetization through lattice expansion. These results not only reveal a hydrogen chemical state beyond anion and cation within the complex oxides, but also suggest an effective pathway to design functional materials through tunable ionic evolution.