Carrier‐Type Modulation and Mobility Improvement of Thin MoTe2

A systematic modulation of the carrier type in molybdenum ditelluride (MoTe₂) field‐effect transistors (FETs) is described, through rapid thermal annealing (RTA) under a controlled O₂ environment (p‐type modulation) and benzyl viologen (BV) doping (n‐type modulation). Al₂O₃ capping is then introduced to improve the carrier mobilities and device stability. MoTe₂ is found to be ultrasensitive to O₂ at elevated temperatures (250 °C). Charge carriers of MoTe₂ flakes annealed via RTA at various vacuum levels are tuned between predominantly pristine n‐type ambipolar, symmetric ambipolar, unipolar p‐type, and degenerate‐like p‐type. Changes in the MoTe₂‐transistor performance are confirmed to originate from the physical and chemical absorption and dissociation of O₂, especially at tellurium vacancy sites. The electron branch is modulated by varying the BV dopant concentrations and annealing conditions. Unipolar n‐type MoTe₂ FETs with a high on–off ratio exceeding 10⁶ are achieved under optimized doping conditions. By introducing Al₂O₃ capping, carrier field effect mobilities (41 for holes and 80 cm² V^?1 s^?1 for electrons) and device stability are improved due to the reduced trap densities and isolation from ambient air. Lateral MoTe₂ p–n diodes with an ideality factor of 1.2 are fabricated using the p‐ and n‐type doping technique to test the superb potential of the doping method in functional electronic device applications.     

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.     

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.     

Extraordinary n‐Type Mg3SbBi Thermoelectrics Enabled by Yttrium Doping

Advancing thermoelectric n‐type Mg₃Sb₂ alloys requires both high carrier concentration offered by effective doping and high carrier mobility enabled by large grains. Existing research usually involves chalcogen doping on the anion sites, and the resultant carrier concentration reaches ≈3 × 10¹⁹ cm^?3 or below. This is much lower than the optimum theoretically predicted, which suggets that further improvements will be possible once a highly efficient dopant is found. Yttrium, a trivalent dopant, is shown to enable carrier concentrations up to and above ≈1 × 10²⁰ cm^?3 when it is doped on the cation site. Such carrier concentration allows for in‐depth understand of the electronic transport properties over a broad range of carrier concentrations, based on a single parabolic band approximation. As well as reasonably high carrier mobility in coarse‐grain materials sintered by hot deforming and fusing of large pieces of ingots synthesized by melting, higher thermoelectric performance than earlier experimentally reported for n‐type Mg₃Sb₂ is found. In particular, the thermoelectric figure of merit, zT, is even higher than that of any known n‐type thermoelectric, including Bi₂Te₃ alloys, within 300–500 K. This might pave the way for Mg₃Sb₂ alloys to become a realistic material for n‐type thermoelectrics for sustainable applications.     

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.     

Earth‐Abundant Chalcogenide Photovoltaic Devices with over 5% Efficiency Based on a Cu2BaSn(S,Se)4 Absorber

In recent years, Cu₂ZnSn(S,Se)₄ (CZTSSe) materials have enabled important progress in associated thin‐film photovoltaic (PV) technology, while avoiding scarce and/or toxic metals; however, cationic disorder and associated band tailing fundamentally limit device performance. Cu₂BaSnS₄ (CBTS) has recently been proposed as a prospective alternative large bandgap (~2 eV), environmentally friendly PV material, with ~2% power conversion efficiency (PCE) already demonstrated in corresponding devices. In this study, a two‐step process (i.e., precursor sputter deposition followed by successive sulfurization/selenization) yields high‐quality nominally pinhole‐free films with large (>1 µm) grains of selenium‐incorporated (x = 3) Cu₂BaSnS_4?x Se_x (CBTSSe) for high‐efficiency PV devices. By incorporating Se in the sulfide film, absorber layers with 1.55 eV bandgap, ideal for single‐junction PV, have been achieved within the CBTSSe trigonal structural family. The abrupt transition in quantum efficiency data for wavelengths above the absorption edge, coupled with a strong sharp photoluminescence feature, confirms the relative absence of band tailing in CBTSSe compared to CZTSSe. For the first time, by combining bandgap tuning with an air‐annealing step, a CBTSSe‐based PV device with 5.2% PCE (total area 0.425 cm²) is reported, >2.5× better than the previous champion pure sulfide device. These results suggest substantial promise for the emerging Se‐rich Cu₂BaSnS_4–x Se_x family for high‐efficiency and earth‐abundant PV.     

Solution Combustion Synthesis: Low‐Temperature Processing for p‐Type Cu:NiO Thin Films for Transparent Electronics

Low‐temperature solution processing opens a new window for the fabrication of oxide semiconductors due to its simple, low cost, and large‐area uniformity. Herein, by using solution combustion synthesis (SCS), p‐type Cu‐doped NiO (Cu:NiO) thin films are fabricated at a temperature lower than 150 °C. The light doping of Cu substitutes the Ni site and disperses the valence band of the NiO matrix, leading to an enhanced p‐type conductivity. Their integration into thin‐film transistors (TFTs) demonstrates typical p‐type semiconducting behavior. The optimized Cu_5%NiO TFT exhibits outstanding electrical performance with a hole mobility of 1.5 cm² V^?1 s^?1, a large on/off current ratio of ≈10⁴, and clear switching characteristics under dynamic measurements. The employment of a high‐k ZrO₂ gate dielectric enables a low operating voltage (≤2 V) of the TFTs, which is critical for portable and battery‐driven devices. The construction of a light‐emitting‐diode driving circuit demonstrates the high current control capability of the resultant TFTs. The achievement of the low‐temperature‐processed Cu:NiO thin films via SCS not only provides a feasible approach for low‐cost flexible p‐type oxide electronics but also represents a significant step toward the development of complementary metal–oxide semiconductor circuits.     

N‐Doped Graphene Field‐Effect Transistors with Enhanced Electron Mobility and Air‐Stability

Although graphene can be easily p‐doped by various adsorbates, developing stable n‐doped graphene that is very useful for practical device applications is a difficult challenge. We investigated the doping effect of solution‐processed (4‐(1,3‐dimethyl‐2,3‐dihydro‐1H‐benzoimidazol‐2‐yl)phenyl)dimethylamine (N‐DMBI) on chemical‐vapor‐deposited (CVD) graphene. Strong n‐type doping is confirmed by Raman spectroscopy and the electrical transport characteristics of graphene field‐effect transistors. The strong n‐type doping effect shifts the Dirac point to around ‐140 V. Appropriate annealing at a low temperature of 80 ºC enables an enhanced electron mobility of 1150 cm² V^?1 s^?1. The work function and its uniformity on a large scale (1.2 mm × 1.2 mm) of the doped surface are evaluated using ultraviolet photoelectron spectroscopy and Kelvin probe mapping. Stable electrical properties are observed in a device aged in air for more than one month.     

Controllable,Wide‐Ranging n‐Doping and p‐Doping of Monolayer Group 6 Transition‐Metal Disulfides and Diselenides

Developing processes to controllably dope transition‐metal dichalcogenides (TMDs) is critical for optical and electrical applications. Here, molecular reductants and oxidants are introduced onto monolayer TMDs, specifically MoS₂, WS₂, MoSe₂, and WSe₂. Doping is achieved by exposing the TMD surface to solutions of pentamethylrhodocene dimer as the reductant (n‐dopant) and “Magic Blue,” [N(C₆H₄‐p‐Br)₃]SbCl₆, as the oxidant (p‐dopant). Current–voltage characteristics of field‐effect transistors show that, regardless of their initial transport behavior, all four TMDs can be used in either p‐ or n‐channel devices when appropriately doped. The extent of doping can be controlled by varying the concentration of dopant solutions and treatment time, and, in some cases, both nondegenerate and degenerate regimes are accessible. For all four TMD materials, the photoluminescence intensity; for all four materials the PL intensity is enhanced with p‐doping but reduced with n‐doping. Raman and X‐ray photoelectron spectroscopy (XPS) also provide insight into the underlying physical mechanism by which the molecular dopants react with the monolayer. Estimates of changes of carrier density from electrical, PL, and XPS results are compared. Overall a simple and effective route to tailor the electrical and optical properties of TMDs is demonstrated.     

Enhancing Molecular n‐Type Doping of Donor–Acceptor Copolymers by Tailoring Side Chains

In this contribution, for the first time, the molecular n‐doping of a donor–acceptor (D–A) copolymer achieving 200‐fold enhancement of electrical conductivity by rationally tailoring the side chains without changing its D–A backbone is successfully improved. Instead of the traditional alkyl side chains for poly{[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl](NDI)‐alt‐5,5′‐(2,2′‐bithiophene)} (N2200), polar triethylene glycol type side chains is utilized and a high electrical conductivity of 0.17 S cm^?1 after doping with (4‐(1,3‐dimethyl‐2,3‐dihydro‐1H‐benzoimidazol‐2‐yl)phenyl)dimethylamine is achieved, which is the highest reported value for n‐type D–A copolymers. Coarse‐grained molecular dynamics simulations indicate that the polar side chains can significantly reduce the clustering of dopant molecules and favor the dispersion of the dopant in the host matrix as compared to the traditional alkyl side chains. Accordingly, intimate contact between the host and dopant molecules in the NDI‐based copolymer with polar side chains facilitates molecular doping with increased doping efficiency and electrical conductivity. For the first time, a heterogeneous thermoelectric transport model for such a material is proposed, that is the percolation of charge carriers from conducting ordered regions through poorly conductive disordered regions, which provides pointers for further increase in the themoelectric properties of n‐type D–A copolymers.     

MOF‐Derived Bifunctional Cu3P Nanoparticles Coated by a N,P‐Codoped Carbon Shell for Hydrogen Evolution and Oxygen Reduction

Metal–organic frameworks (MOFs) have recently emerged as a type of uniformly and periodically atom‐distributed precursor and efficient self‐sacrificial template to fabricate hierarchical porous‐carbon‐related nanostructured functional materials. For the first time, a Cu‐based MOF, i.e., Cu‐NPMOF is used, whose linkers contain nitrogen and phosphorus heteroatoms, as a single precursor and template to prepare novel Cu₃P nanoparticles (NPs) coated by a N,P‐codoped carbon shell that is extended to a hierarchical porous carbon matrix with identical uniform N and P doping (termed Cu₃P@NPPC) as an electrocatalyst. Cu₃P@NPPC demonstrates outstanding activity for both the hydrogen evolution and oxygen reduction reaction, representing the first example of a Cu₃P‐based bifunctional catalyst for energy‐conversion reactions. The high performances are ascribed to the high specific surface area, the synergistic effects of the Cu₃P NPs with intrinsic activity, the protection of the carbon shell, and the hierarchical porous carbon matrix doped by multiheteroatoms. This strategy of using a diverse MOF as a structural and compositional material to create a new multifunctional composite/hybrid may expand the opportunities to explore highly efficient and robust non‐noble‐metal catalysts for energy‐conversion reactions.     

Phase Modulation of (1T‐2H)‐MoSe2/TiC‐C Shell/Core Arrays via Nitrogen Doping for Highly Efficient Hydrogen Evolution Reaction

Tailoring molybdenum selenide electrocatalysts with tunable phase and morphology is of great importance for advancement of hydrogen evolution reaction (HER). In this work, phase‐ and morphology‐modulated N‐doped MoSe₂/TiC‐C shell/core arrays through a facile hydrothermal and postannealing treatment strategy are reported. Highly conductive TiC‐C nanorod arrays serve as the backbone for MoSe₂ nanosheets to form high‐quality MoSe₂/TiC‐C shell/core arrays. Impressively, continuous phase modulation of MoSe₂ is realized on the MoSe₂/TiC‐C arrays. Except for the pure 1T‐MoSe₂ and 2H‐MoSe₂, mixed (1T‐2H)‐MoSe₂ nanosheets are achieved in the N‐MoSe₂ by N doping and demonstrated by spherical aberration electron microscope. Plausible mechanism of phase transformation and different doping sites of N atom are proposed via theoretical calculation. The much smaller energy barrier, longer H? Se bond length, and diminished bandgap endow N‐MoSe₂/TiC‐C arrays with substantially superior HER performance compared to 1T and 2H phase counterparts. Impressively, the designed N‐MoSe₂/TiC‐C arrays exhibit a low overpotential of 137 mV at a large current density of 100 mA cm^?2, and a small Tafel slope of 32 mV dec^?1. Our results pave the way to unravel the enhancement mechanism of HER on 2D transition metal dichalcogenides by N doping.     

n‐Type Doped Conjugated Polymer for Nonvolatile Memory

This study demonstrates a facile way to efficiently induce strong memory behavior from common p‐type conjugated polymers by adding n‐type dopant 2‐(2‐methoxyphenyl)‐1,3‐dimethyl‐2,3‐dihydro‐1H‐benzoimidazole. The n‐type doped p‐channel conjugated polymers not only enhance n‐type charge transport characteristics of the polymers, but also facilitate to storage charges and cause reversible bistable (ON and OFF states) switching upon application of gate bias. The n‐type doped memory shows a large memory window of up to 47 V with an on/off current ratio larger than 10 000. The charge retention time can maintain over 100 000 s. Similar memory behaviors are also observed in other common semiconducting polymers such as poly(3‐hexyl thiophene) and poly[2,5‐bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐b]thiophene], and a high mobility donor–acceptor polymer, poly(isoindigo‐bithiophene). In summary, these observations suggest that this approach is a general method to induce memory behavior in conjugated polymers. To the best of the knowledge, this is the first report for p‐type polymer memory achieved using n‐type charge‐transfer doping.     

N‐Type Superconductivity in an Organic Mott Insulator Induced by Light‐Driven Electron‐Doping

The presence of interface dipoles in self‐assembled monolayers (SAMs) gives rise to electric‐field effects at the device interfaces. SAMs of spiropyran derivatives can be used as photoactive interface dipole layer in field‐effect transistors because the photochromism of spiropyrans involves a large dipole moment switching. Recently, light‐induced p‐type superconductivity in an organic Mott insulator, κ‐(BEDT‐TTF)₂Cu[N(CN)₂]Br (κ‐Br: BEDT‐TTF = bis(ethylenedithio)tetrathiafulvalene) has been realized, thanks to the hole carriers induced by significant interface dipole variation in the spiropyran‐SAM. This report explores the converse situation by designing a new type of spiropyran monolayer in which light‐induced electron‐doping into κ‐Br and accompanying n‐type superconducting transition have been observed. These results open new possibilities for novel electronics utilizing a photoactive SAMs, which can design not only the magnitude but also the direction of photoinduced electric‐fields at the device interfaces.     

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.     

Modulation‐Doped In2O3/ZnO Heterojunction Transistors Processed from Solution

This paper reports the controlled growth of atomically sharp In₂O₃/ZnO and In₂O₃/Li‐doped ZnO (In₂O₃/Li‐ZnO) heterojunctions via spin‐coating at 200 °C and assesses their application in n‐channel thin‐film transistors (TFTs). It is shown that addition of Li in ZnO leads to n‐type doping and allows for the accurate tuning of its Fermi energy. In the case of In₂O₃/ZnO heterojunctions, presence of the n‐doped ZnO layer results in an increased amount of electrons being transferred from its conduction band minimum to that of In₂O₃ over the interface, in a process similar to modulation doping. Electrical characterization reveals the profound impact of the presence of the n‐doped ZnO layer on the charge transport properties of the isotype In₂O₃/Li‐ZnO heterojunctions as well as on the operating characteristics of the resulting TFTs. By judicious optimization of the In₂O₃/Li‐ZnO interface microstructure, and Li concentration, significant enhancement in both the electron mobility and TFT bias stability is demonstrated.     

Room‐Temperature Solution‐Synthesized p‐Type Copper(I) Iodide Semiconductors for Transparent Thin‐Film Transistors and Complementary Electronics

Here, room‐temperature solution‐processed inorganic p‐type copper iodide (CuI) thin‐film transistors (TFTs) are reported for the first time. The spin‐coated 5 nm thick CuI film has average hole mobility (µ_FE) of 0.44 cm² V^?1 s^?1 and on/off current ratio of 5 × 10². Furthermore, µ_FE increases to 1.93 cm² V^?1 s^?1 and operating voltage significantly reduces from 60 to 5 V by using a high permittivity ZrO₂ dielectric layer replacing traditional SiO₂. Transparent complementary inverters composed of p‐type CuI and n‐type indium gallium zinc oxide TFTs are demonstrated with clear inverting characteristics and voltage gain over 4. These outcomes provide effective approaches for solution‐processed inorganic p‐type semiconductor inks and related electronics.     

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.     

High‐Performance n‐Channel Organic Transistors Using High‐Molecular‐Weight Electron‐Deficient Copolymers and Amine‐Tailed Self‐Assembled Monolayers

While high‐performance p‐type semiconducting polymers are widely reported, their n‐type counterparts are still rare in terms of quantity and quality. Here, an improved Stille polymerization protocol using chlorobenzene as the solvent and palladium(0)/copper(I) as the catalyst is developed to synthesize high‐quality n‐type polymers with number‐average molecular weight up to 10⁵ g mol^?1. Furthermore, by sp²‐nitrogen atoms (sp²‐N) substitution, three new n‐type polymers, namely, pBTTz, pPPT, and pSNT, are synthesized, and the effect of different sp²‐N substitution positions on the device performances is studied for the first time. It is found that the incorporation of sp²‐N into the acceptor units rather than the donor units results in superior crystalline microstructures and higher electron mobilities. Furthermore, an amine‐tailed self‐assembled monolayer (SAM) is smoothly formed on a Si/SiO₂ substrate by a simple spin‐coating technique, which can facilitate the accumulation of electrons and lead to more perfect unipolar n‐type transistor performances. Therefore, a remarkably high unipolar electron mobility up to 5.35 cm² V^?1 s^?1 with a low threshold voltage (≈1 V) and high on/off current ratio of ≈10⁷ is demonstrated for the pSNT‐based devices, which are among the highest values for unipolar n‐type semiconducting polymers.     

Classification of Lattice Defects in the Kesterite Cu2ZnSnS4 and Cu2ZnSnSe4 Earth‐Abundant Solar Cell Absorbers

The kesterite‐structured semiconductors Cu₂ZnSnS₄ and Cu₂ZnSnSe₄ are drawing considerable attention recently as the active layers in earth‐abundant low‐cost thin‐film solar cells. The additional number of elements in these quaternary compounds, relative to binary and ternary semiconductors, results in increased flexibility in the material properties. Conversely, a large variety of intrinsic lattice defects can also be formed, which have important influence on their optical and electrical properties, and hence their photovoltaic performance. Experimental identification of these defects is currently limited due to poor sample quality. Here recent theoretical research on defect formation and ionization in kesterite materials is reviewed based on new systematic calculations, and compared with the better studied chalcopyrite materials CuGaSe₂ and CuInSe₂. Four features are revealed and highlighted: (i) the strong phase‐competition between the kesterites and the coexisting secondary compounds; (ii) the intrinsic p‐type conductivity determined by the high population of acceptor Cu_Zn antisites and Cu vacancies, and their dependence on the Cu/(Zn+Sn) and Zn/Sn ratio; (iii) the role of charge‐compensated defect clusters such as [2Cu_Zn+Sn_Zn], [V_Cu+Zn_Cu] and [Zn_Sn+2Zn_Cu] and their contribution to non‐stoichiometry; (iv) the electron‐trapping effect of the abundant [2Cu_Zn+Sn_Zn] clusters, especially in Cu₂ZnSnS₄. The calculated properties explain the experimental observation that Cu poor and Zn rich conditions (Cu/(Zn+Sn) ≈ 0.8 and Zn/Sn ≈ 1.2) result in the highest solar cell efficiency, as well as suggesting an efficiency limitation in Cu₂ZnSn(S,Se)₄ cells when the S composition is high.