Chemically Tuned p‐ and n‐Type WSe2 Monolayers with High Carrier Mobility for Advanced Electronics

Monolayers of transition metal dichalcogenides (TMDCs) have attracted a great interest for post‐silicon electronics and photonics due to their high carrier mobility, tunable bandgap, and atom‐thick 2D structure. With the analogy to conventional silicon electronics, establishing a method to convert TMDC to p‐ and n‐type semiconductors is essential for various device applications, such as complementary metal‐oxide‐semiconductor (CMOS) circuits and photovoltaics. Here, a successful control of the electrical polarity of monolayer WSe₂ is demonstrated by chemical doping. Two different molecules, 4‐nitrobenzenediazonium tetrafluoroborate and diethylenetriamine, are utilized to convert ambipolar WSe₂ field‐effect transistors (FETs) to p‐ and n‐type, respectively. Moreover, the chemically doped WSe₂ show increased effective carrier mobilities of 82 and 25 cm² V^?1s^?1 for holes and electrons, respectively, which are much higher than those of the pristine WSe₂. The doping effects are studied by photoluminescence, Raman, X‐ray photoelectron spectroscopy, and density functional theory. Chemically tuned WSe₂ FETs are integrated into CMOS inverters, exhibiting extremely low power consumption ( ≈ 0.17 nW). Furthermore, a p‐n junction within single WSe₂ grain is realized via spatially controlled chemical doping. The chemical doping method for controlling the transport properties of WSe₂ will contribute to the development of TMDC‐based advanced electronics.     

MoTe2 p–n Homojunctions Defined by Ferroelectric Polarization

Doped p–n junctions are fundamental electrical components in modern electronics and optoelectronics. Due to the development of device miniaturization, the emergence of two-dimensional (2D) materials may initiate the next technological leap toward the post-Moore era owing to their unique structures and physical properties. The purpose of fabricating 2D p–n junctions has fueled many carrier-type modulation methods, such as electrostatic doping, surface modification, and element intercalation. Here, by using the nonvolatile ferroelectric field polarized in the opposite direction, efficient carrier modulation in ambipolar molybdenum telluride (MoTe₂) to form a p–n homojunction at the domain wall is demonstrated. The nonvolatile MoTe₂ p–n junction can be converted to n–p, n–n, and p–p configurations by external gate voltage pulses. Both rectifier diodes exhibited excellent rectifying characteristics with a current on/off ratio of 5 × 10⁵. As a photodetector/photovoltaic, the device presents responsivity of 5 A W⁻¹, external quantum efficiency of 40%, specific detectivity of 3 × 10¹² Jones, fast response time of 30 µs, and power conversion efficiency of 2.5% without any bias or gate voltages. The MoTe₂ p–n junction presents an obvious short-wavelength infrared photoresponse at room temperature, complementing the current infrared photodetectors with the inadequacies of complementary metal-oxide-semiconductor incompatibility and cryogenic operation temperature.     

Controllable P‐ and N‐Type Conversion of MoTe2 via Oxide Interfacial Layer for Logic Circuits

To realize basic electronic units such as complementary metal‐oxide‐semiconductor (CMOS) inverters and other logic circuits, the selective and controllable fabrication of p‐ and n‐type transistors with a low Schottky barrier height is highly desirable. Herein, an efficient and nondestructive technique of electron‐charge transfer doping by depositing a thin Al₂O₃ layer on chemical vapor deposition (CVD)‐grown 2H‐MoTe₂ is utilized to tune the doping from p‐ to n‐type. Moreover, a type‐controllable MoTe₂ transistor with a low Schottky barrier height is prepared. The selectively converted n‐type MoTe₂ transistor from the p‐channel exhibits a maximum on‐state current of 10 µA, with a higher electron mobility of 8.9 cm² V^?1 s^?1 at a drain voltage (V_ds) of 1 V with a low Schottky barrier height of 28.4 meV. To validate the aforementioned approach, a prototype homogeneous CMOS inverter is fabricated on a CVD‐grown 2H‐MoTe₂ single crystal. The proposed inverter exhibits a high DC voltage gain of 9.2 with good dynamic behavior up to a modulation frequency of 1 kHz. The proposed approach may have potential for realizing future 2D transition metal dichalcogenide‐based efficient and ultrafast electronic units with high‐density circuit components under a low‐dimensional regime.     

Reversible and Precisely Controllable p/n‐Type Doping of MoTe2 Transistors through Electrothermal Doping

Precisely controllable and reversible p/n‐type electronic doping of molybdenum ditelluride (MoTe₂) transistors is achieved by electrothermal doping (E‐doping) processes. E‐doping includes electrothermal annealing induced by an electric field in a vacuum chamber, which results in electron (n‐type) doping and exposure to air, which induces hole (p‐type) doping. The doping arises from the interaction between oxygen molecules or water vapor and defects of tellurium at the MoTe₂ surface, and allows the accurate manipulation of p/n‐type electrical doping of MoTe₂ transistors. Because no dopant or special gas is used in the E‐doping processes of MoTe₂, E‐doping is a simple and efficient method. Moreover, through exact manipulation of p/n‐type doping of MoTe₂ transistors, quasi‐complementary metal oxide semiconductor adaptive logic circuits, such as an inverter, not or gate, and not and gate, are successfully fabricated. The simple method, E‐doping, adopted in obtaining p/n‐type doping of MoTe₂ transistors undoubtedly has provided an approach to create the electronic devices with desired performance.     

Homogeneous 2D MoTe2 p–n Junctions and CMOS Inverters formed by Atomic‐Layer‐Deposition‐Induced Doping

Recently, α‐MoTe₂, a 2D transition‐metal dichalcogenide (TMD), has shown outstanding properties, aiming at future electronic devices. Such TMD structures without surface dangling bonds make the 2D α‐MoTe₂ a more favorable candidate than conventional 3D Si on the scale of a few nanometers. The bandgap of thin α‐MoTe₂ appears close to that of Si and is quite smaller than those of other typical TMD semiconductors. Even though there have been a few attempts to control the charge‐carrier polarity of MoTe₂, functional devices such as p–n junction or complementary metal–oxide–semiconductor (CMOS) inverters have not been reported. Here, we demonstrate a 2D CMOS inverter and p–n junction diode in a single α‐MoTe₂ nanosheet by a straightforward selective doping technique. In a single α‐MoTe₂ flake, an initially p‐doped channel is selectively converted to an n‐doped region with high electron mobility of 18 cm² V^?1 s^?1 by atomic‐layer‐deposition‐induced H‐doping. The ultrathin CMOS inverter exhibits a high DC voltage gain of 29, an AC gain of 18 at 1 kHz, and a low static power consumption of a few nanowatts. The results show a great potential of α‐MoTe₂ for future electronic devices based on 2D semiconducting materials.     

Anti‐Ambipolar Transport with Large Electrical Modulation in 2D Heterostructured Devices

Van der Waals materials and their heterostructures provide a versatile platform to explore new device architectures and functionalities beyond conventional semiconductors. Of particular interest is anti‐ambipolar behavior, which holds potentials for various digital electronic applications. However, most of the previously conducted studies are focused on hetero‐ or homo‐ p–n junctions, which suffer from a weak electrical modulation. Here, the anti‐ambipolar transport behavior and negative transconductance of MoTe₂ transistors are reported using a graphene/h‐BN floating‐gate structure to dynamically modulate the conduction polarity. Due to the asymmetric electrical field regulating effect on the recombination and diffusion currents, the anti‐ambipolar transport and negative transconductance feature can be systematically controlled. Consequently, the device shows an unprecedented peak resistance modulation factor (≈5 × 10³), and effective photoexcitation modulation with distinct threshold voltage shift and large photo on/off ratio (≈10⁴). Utilizing this large modulation effect, the voltage‐transfer characteristics of an inverter circuit variant are further studied and its applications in Schmitt triggers and multivalue output are further explored. These properties, in addition to their proven nonvolatile storage, suggest that such 2D heterostructured devices display promising perspectives toward future logic applications.     

Homogeneous 2D MoTe2 CMOS Inverters and p–n Junctions Formed by Laser‐Irradiation‐Induced p‐Type Doping

Among all typical transition‐metal dichalcogenides (TMDs), the bandgap of α‐MoTe₂ is smallest and is close to that of conventional 3D Si. The properties of α‐MoTe₂ make it a favorable candidate for future electronic devices. Even though there are a few reports regarding fabrication of complementary metal–oxide‐semiconductor (CMOS) inverters or p–n junction by controlling the charge‐carrier polarity of TMDs, the fabrication process is complicated. Here, a straightforward selective doping technique is demonstrated to fabricate a 2D p–n junction diode and CMOS inverter on a single α‐MoTe₂ nanoflake. The n‐doped channel of a single α‐MoTe₂ nanoflake is selectively converted to a p‐doped region via laser‐irradiation‐induced MoO_x doping. The homogeneous 2D MoTe₂ CMOS inverter has a high DC voltage gain of 28, desirable noise margin (NM_H = 0.52 V_DD, NM_L = 0.40 V_DD), and an AC gain of 4 at 10 kHz. The results show that the doping technique by laser scan can be potentially used for future larger‐scale MoTe₂ CMOS circuits.     

Impact of H‐Doping on n‐Type TMD Channels for Low‐Temperature Band‐Like Transport

Band‐like transport behavior of H‐doped transition metal dichalcogenide (TMD) channels in field effect transistors (FET) is studied by conducting low‐temperature electrical measurements, where MoTe₂, WSe₂, and MoS₂ are chosen for channels. Doped with H atoms through atomic layer deposition, those channels show strong n‐type conduction and their mobility increases without losing on‐state current as the measurement temperature decreases. In contrast, the mobility of unintentionally (naturally) doped TMD FETs always drops at low temperatures whether they are p‐ or n‐type. Density functional theory calculations show that H‐doped MoTe₂, WSe₂, and MoS₂ have Fermi levels above conduction band edge. It is thus concluded that the charge transport behavior in H‐doped TMD channels is metallic showing band‐like transport rather than thermal hopping. These results indicate that H‐doped TMD FETs are practically useful even at low‐temperature ranges.     

A Fermi‐Level‐Pinning‐Free 1D Electrical Contact at the Intrinsic 2D MoS2–Metal Junction

Currently 2D crystals are being studied intensively for use in future nanoelectronics, as conventional semiconductor devices face challenges in high power consumption and short channel effects when scaled to the quantum limit. Toward this end, achieving barrier‐free contact to 2D semiconductors has emerged as a major roadblock. In conventional contacts to bulk metals, the 2D semiconductor Fermi levels become pinned inside the bandgap, deviating from the ideal Schottky–Mott rule and resulting in significant suppression of carrier transport in the device. Here, MoS₂ polarity control is realized without extrinsic doping by employing a 1D elemental metal contact scheme. The use of high‐work‐function palladium (Pd) or gold (Au) enables a high‐quality p‐type dominant contact to intrinsic MoS₂, realizing Fermi level depinning. Field‐effect transistors (FETs) with Pd edge contact and Au edge contact show high performance with the highest hole mobility reaching 330 and 432 cm² V^?1 s^?1 at 300 K, respectively. The ideal Fermi level alignment allows creation of p‐ and n‐type FETs on the same intrinsic MoS₂ flake using Pd and low‐work‐function molybdenum (Mo) contacts, respectively. This device acts as an efficient inverter, a basic building block for semiconductor integrated circuits, with gain reaching 15 at V_D = 5 V.     

2D Molecular Crystal Bilayer p–n Junctions: A General Route toward High‐Performance and Well‐Balanced Ambipolar Organic Field‐Effect Transistors

Ambipolar organic field‐effect transistors (OFETs) are vital for the construction of high‐performance all‐organic digital circuits. The bilayer p–n junction structure, which is composed of separate layers of p‐ and n‐type organic semiconductors, is considered a promising way to realize well‐balanced ambipolar charge transport. However, this approach suffers from severely reduced mobility due to the rough interface between the polycrystalline thin films of p‐ and n‐type organic semiconductors. Herein, 2D molecular crystal (2DMC) bilayer p–n junctions are proposed to construct high‐performance and well‐balanced ambipolar OFETs. The molecular‐scale thickness of the 2DMC ensures high injection efficiency and the atomically flat surface of the 2DMC leads to high‐quality p‐ and n‐layer interfaces. Moreover, by controlling the layer numbers of the p‐ and n‐type 2DMCs, the electron and hole mobilities are tuned and well‐balanced ambipolar transport is accomplished. The hole and electron mobilities reach up to 0.87 and 0.82 cm² V^?1 s^?1, respectively, which are the highest values among organic single‐crystalline double‐channel OFETs measured in ambient air. This work provides a general route to construct high‐performance and well‐balanced ambipolar OFETs based on available unipolar materials.     

Efficient Self‐Driven Photodetectors Featuring a Mixed‐Dimensional van der Waals Heterojunction Formed from a CdS Nanowire and a MoTe2 Flake

Heterojunctions formed from low‐dimensional materials can result in photovoltaic and photodetection devices displaying exceptional physical properties and excellent performance. Herein, a mixed‐dimensional van der Waals (vdW) heterojunction comprising a 1D n‐type Ga‐doped CdS nanowire and a 2D p‐type MoTe₂ flake is demonstrated; the corresponding photovoltaic device exhibits an outstanding conversion efficiency of 15.01% under illumination with white light at 650 µW cm^?2. A potential difference of 80 meV measured, using Kelvin probe force microscopy, at the CdS–MoTe₂ interface confirms the separation and accumulation of photoexcited carriers upon illumination. Moreover, the photodetection characteristics of the vdW heterojunction device at zero bias reveal a rapid response time (<50 ms) and a photoresponsivity that are linearly proportional to the power density of the light. Interestingly, the response of the vdW heterojunction device is negligible when illuminated at 580 nm; this exceptional behavior is presumably due to the rapid rate of recombination of the photoexcited carriers of MoTe₂. Such mixed‐dimensional vdW heterojunctions appear to be novel design elements for efficient photovoltaic and self‐driven photodetection devices.     

Ultrahigh‐Sensitive Broadband Photodetectors Based on Dielectric Shielded MoTe2/Graphene/SnS2 p–g–n Junctions

2D atomic sheets of transition metal dichalcogenides (TMDs) have a tremendous potential for next‐generation optoelectronics since they can be stacked layer‐by‐layer to form van der Waals (vdW) heterostructures. This allows not only bypassing difficulties in heteroepitaxy of lattice‐mismatched semiconductors of desired functionalities but also providing a scheme to design new optoelectronics that can surpass the fundamental limitations on their conventional semiconductor counterparts. Herein, a novel 2D h‐BN/p‐MoTe₂/graphene/n‐SnS₂/h‐BN p–g–n junction, fabricated by a layer‐by‐layer dry transfer, demonstrates high‐sensitivity, broadband photodetection at room temperature. The combination of the MoTe₂ and SnS₂ of complementary bandgaps, and the graphene interlayer provides a unique vdW heterostructure with a vertical built‐in electric field for high‐efficiency broadband light absorption, exciton dissociation, and carrier transfer. The graphene interlayer plays a critical role in enhancing sensitivity and broadening the spectral range. An optimized device containing 5?7‐layer graphene has been achieved and shows an extraordinary responsivity exceeding 2600 A W^?1 with fast photoresponse and specific detectivity up to ≈10¹³ Jones in the ultraviolet–visible–near‐infrared spectrum. This result suggests that the vdW p–g–n junctions containing multiple photoactive TMDs can provide a viable approach toward future ultrahigh‐sensitivity and broadband photonic detectors.     

High-Performance CMOS Inverter Array with Monolithic 3D Architecture Based on CVD-Grown n-MoS2 and p-MoTe2

In this work, monolithic three-dimensional complementary metal oxide semiconductor (CMOS) inverter array has been fabricated, based on large-scale n-MoS₂ and p-MoTe₂ grown by the chemical vapor deposition method. In the CMOS device, the n- and p-channel field-effect transistors (FETs) stack vertically and share the same gate electrode. High k HfO₂ is used as the gate dielectric. An Al₂O₃ seed layer is used to protect the MoS₂ from heavily n-doping in the later-on atomic layer deposition process. P-MoTe₂ FET is intentionally designed as the upper layer. Because p-doping of MoTe₂ results from oxygen and water in the air, this design can guarantee a higher hole density of MoTe₂. An HfO₂ capping layer is employed to further balance the transfer curves of n- and p-channel FETs and improve the performance of the inverter. The typical gain and power consumption of the CMOS devices are about 4.2 and 0.11 nW, respectively, at V_DD of 1 V. The statistical results show that the CMOS array is with high device yield (60%) and an average voltage gain value of about 3.6 at V_DD of 1 V. This work demonstrates the advantage of two-dimensional semi-conductive transition metal dichalcogenides in fabricating high-density integrated circuits.     

Isoindigo‐Based Polymers with Small Effective Masses for High‐Mobility Ambipolar Field‐Effect Transistors

So far, most of the reported high‐mobility conjugated polymers are p‐type semiconductors. By contrast, the advances in high‐mobility ambipolar polymers fall greatly behind those of p‐type counterparts. Instead of unipolar p‐type and n‐type materials, ambipolar polymers, especially balanced ambipolar polymers, are potentially serviceable for easy‐fabrication and low‐cost complementary metal‐oxide‐semiconductor circuits. Therefore, it is a critical issue to develop high‐mobility ambipolar polymers. Here, three isoindigo‐based polymers, PIID‐2FBT , P1FIID‐2FBT , and P2FIID‐2FBT are developed for high‐performance ambipolar organic field‐effect transistors. After the incorporation of fluorine atoms, the polymers exhibit enhanced coplanarity, lower energy levels, higher crystallinity, and thus increased µ _e. P2FIID‐2FBT exhibits n‐type dominant performance with a µ _e of 9.70 cm² V^?1 s^?1. Moreover, P1FIID‐2FBT exhibits a highly balanced µ _h and µ _e of 6.41 and 6.76 cm² V^?1 s^?1, respectively, which are among the highest values for balanced ambipolar polymers. Moreover, a concept “effective mass” is introduced to further study the reasons for the high performance of the polymers. All the polymers have small effective masses, indicating good intramolecular charge transport. The results demonstrate that high‐mobility ambipolar semiconductors can be obtained by designing polymers with fine‐tuned energy levels, small effective masses, and high crystallinity.     

Fine-grained polycrystalline MoTe2 with enhanced thermoelectric properties through iodine doping

Consisting of heavy elements and favorable electronic structure, MoTe₂ has great potential as a good thermoelectric material for heat-to-electricity conversion. While some experimental work has been performed on the p-type version, n-type MoTe₂ is theoretically predicted to have a great conversion efficiency and is crucial for eventual device functionality, yet has not been explored. Here, the preparation and thermoelectric properties of n-type iodine-doped nano-polycrystalline MoTe₂ are currently reported. Nano-polycrystalline MoTe_2???xI_x is obtained by ball milling and spark plasma sintering techniques. The composition, morphology and crystal structure of the prepared materials were analyzed by XRD and FESEM, which indicated a homogeneous single phase. The measured transport properties over the temperature range of 298–823 K indicate that iodine doping greatly enhances the carrier concentration and corresponding power factor, and drastically reducing the thermal conductivity. The ECR (Electrical conductivity ratios) carrier scattering analysis demonstrates that dislocation scattering is the main mechanism throughout the experimental temperature range. With the temperature and doping increasing, the thermal conductivity was reduced rapidly, and the minimum value was 1.19 Wm^??1 K^??1 at 673 K. The maximum value of the figure merit ZT?~?0.16 over 673–750 K, which is much higher than other reported values. These excellent properties imply that MoTe₂ will be an efficient candidate for thermoelectric applications.

     

Molecular Beam Epitaxy Scalable Growth of Wafer‐Scale Continuous Semiconducting Monolayer MoTe2 on Inert Amorphous Dielectrics

Monolayer MoTe₂, with the narrowest direct bandgap of ≈1.1 eV among Mo‐ and W‐based transition metal dichalcogenides, has attracted increasing attention as a promising candidate for applications in novel near‐infrared electronics and optoelectronics. Realizing 2D lateral growth is an essential prerequisite for uniform thickness and property control over the large scale, while it is not successful yet. Here, layer‐by‐layer growth of 2 in. wafer‐scale continuous monolayer 2H‐MoTe₂ films on inert SiO₂ dielectrics by molecular beam epitaxy is reported. A single‐step Mo‐flux controlled nucleation and growth process is developed to suppress island growth. Atomically flat 2H‐MoTe₂ with 100% monolayer coverage is successfully grown on inert 2 in. SiO₂/Si wafer, which exhibits highly uniform in‐plane structural continuity and excellent phonon‐limited carrier transport behavior. The dynamics‐controlled growth recipe is also extended to fabricate continuous monolayer 2H‐MoTe₂ on atomic‐layer‐deposited Al₂O₃ dielectric. With the breakthrough in growth of wafer‐scale continuous 2H‐MoTe₂ monolayers on device compatible dielectrics, batch fabrication of high‐mobility monolayer 2H‐MoTe₂ field‐effect transistors and the three‐level integration of vertically stacked monolayer 2H‐MoTe₂ transistor arrays for 3D circuitry are successfully demonstrated. This work provides novel insights into the scalable synthesis of monolayer 2H‐MoTe₂ films on universal substrates and paves the way for the ultimate miniaturization of electronics.     

An Ambipolar Superconducting Field‐Effect Transistor Operating above Liquid Helium Temperature

Superconducting (SC) devices are attracting renewed attention as the demands for quantum‐information processing, meteorology, and sensing become advanced. The SC field‐effect transistor (FET) is one of the elements that can control the SC state, but its variety is still limited. Superconductors at the strong‐coupling limit tend to require a higher carrier density when the critical temperature (T_C) becomes higher. Therefore, field‐effect control of superconductivity by a solid gate dielectric has been limited only to low temperatures. However, recent efforts have resulted in achieving n‐type and p‐type SC FETs based on organic superconductors whose T_C exceed liquid He temperature (4.2 K). Here, a novel “ambipolar” SC FET operating at normally OFF mode with T_C of around 6 K is reported. Although this is the second example of an SC FET with such an operation mode, the operation temperature exceeds that of the first example, or magic‐angle twisted‐bilayer graphene that operates at around 1 K. Because the superconductivity in this SC FET is of unconventional type, the performance of the present device will contribute not only to fabricating SC circuits, but also to elucidating phase transitions of strongly correlated electron systems.     

High‐Mobility p‐Type and n‐Type Copper Nitride Semiconductors by Direct Nitriding Synthesis and In Silico Doping Design

Thin‐film photovoltaics (PV) have emerged as a technology that can meet the growing demands for efficient and low‐cost large‐scale cells. However, the photoabsorbers currently in use contain expensive or toxic elements, and the difficulty in bipolar doping, particularly in a device structure, requires elaborate optimization of the heterostructures for improving the efficiency. This study shows that bipolar doping with high hole and electron mobilities in copper nitride (Cu₃N), composed solely of earth‐abundant and environmentally benign elements, is readily available through a novel gaseous direct nitriding reaction applicable to uniform and large‐area deposition. A high‐quality undoped Cu₃N film is essentially an n‐type semiconductor, while p‐type conductivity is realized by interstitial fluorine doping, as predicted using density functional theory calculations and directly proven by atomically resolved imaging. The synthetic methodology for high‐quality p‐type and n‐type films paves the way for the application of Cu₃N as an alternative absorber in thin‐film PV.     

MoS2/Rubrene van der Waals Heterostructure: Toward Ambipolar Field‐Effect Transistors and Inverter Circuits

2D transition metal dichalcogenides are promising channel materials for the next‐generation electronic device. Here, vertically 2D heterostructures, so called van der Waals solids, are constructed using inorganic molybdenum sulfide (MoS₂) few layers and organic crystal – 5,6,11,12‐tetraphenylnaphthacene (rubrene). In this work, ambipolar field‐effect transistors are successfully achieved based on MoS₂ and rubrene crystals with the well balanced electron and hole mobilities of 1.27 and 0.36 cm² V^?1 s^?1, respectively. The ambipolar behavior is explained based on the band alignment of MoS₂ and rubrene. Furthermore, being a building block, the MoS₂/rubrene ambipolar transistors are used to fabricate CMOS (complementary metal oxide semiconductor) inverters that show good performance with a gain of 2.3 at a switching threshold voltage of ?26 V. This work paves a way to the novel organic/inorganic ultrathin heterostructure based flexible electronics and optoelectronic devices.     

Investigation of Electrode Electrochemical Reactions in CH3NH3PbBr3 Perovskite Single‐Crystal Field‐Effect Transistors

Optoelectronic devices based on metal halide perovskites, including solar cells and light‐emitting diodes, have attracted tremendous research attention globally in the last decade. Due to their potential to achieve high carrier mobilities, organic–inorganic hybrid perovskite materials can enable high‐performance, solution‐processed field‐effect transistors (FETs) for next‐generation, low‐cost, flexible electronic circuits and displays. However, the performance of perovskite FETs is hampered predominantly by device instabilities, whose origin remains poorly understood. Here, perovskite single‐crystal FETs based on methylammonium lead bromide are studied and device instabilities due to electrochemical reactions at the interface between the perovskite and gold source–drain top contacts are investigated. Despite forming the contacts by a gentle, soft lamination method, evidence is found that even at such “ideal” interfaces, a defective, intermixed layer is formed at the interface upon biasing of the device. Using a bottom‐contact, bottom‐gate architecture, it is shown that it is possible to minimize such a reaction through a chemical modification of the electrodes, and this enables fabrication of perovskite single‐crystal FETs with high mobility of up to ≈15 cm² V^?1 s^?1 at 80 K. This work addresses one of the key challenges toward the realization of high‐performance solution‐processed perovskite FETs.