Interlayer Rydberg Trions in 2D Semiconductors

• Interlayer Rydberg trions are charged three-particle excitonic complexes with carriers in separate layers, exhibiting weak binding (∼1 meV) and large spatial extent.
• They are realized in electron–hole bilayers and moiré heterostructures where gate tuning and layer spacing modulate interlayer attraction and intralayer repulsion.
• Spectroscopic and first-principles studies reveal Rydberg scaling in excitonic manifolds, highlighting many-body effects that bridge trion and polaron descriptions.

Interlayer Rydberg trions are charged three-body excitonic complexes in layered semiconductors in which the constituent carriers occupy different layers and the internal state is either weakly bound and spatially extended in a Rydberg-like sense or tied to a Rydberg exciton manifold. The available literature supports two closely related usages. In one, the phrase is a useful conceptual label for equilibrium interlayer trions in electron–hole bilayers, whose weak binding, large spatial extent, and strong tunable interactions resemble Rydberg physics in a solid-state, two-dimensional setting. In the other, it refers to resonances near Rydberg exciton lines in bilayer sensor–sample geometries, although in that context the experimentally visible feature can be better described as a Rydberg attractive polaron rather than a simple three-body bound state (Qi et al., 2023, Bondarev et al., 2017, Christianen et al., 7 Dec 2025).

1. Definition and terminological scope

An interlayer trion is a charged three-particle bound complex in which one carrier is confined in one layer and two like-charge carriers are confined in the other. In transition-metal dichalcogenide heterostructures this can occur as a positive interlayer trion $1e\text{–}2h$ or a negative interlayer trion $2e\text{–}1h$. In electrically controlled electron–hole bilayers, these states are the basic three-body building blocks of a strongly interacting ground-state fluid, and they were explicitly compared with positronium ions and the hydrogen anion because their stability is set by interlayer attraction, intralayer repulsion, and exchange-correlation effects (Qi et al., 2023).

The “Rydberg” qualifier is not a universal label in this literature, but it is physically motivated when the trion is much more weakly bound than the underlying exciton. In the bilayer experiments of MoS$_2$/hBN/WSe$_2$ or MoSe$_2$/hBN/WSe$_2$, the interlayer exciton binding energy is $\varepsilon_x \simeq 42 \pm 5\ \text{meV}$ for monolayer hBN, whereas the interlayer trion binding energy is $\varepsilon_t \simeq 1.1 \pm 0.3\ \text{meV}$. That hierarchy makes the trion comparatively extended and easily ionized, which is why a Rydberg-type analogy is useful there (Qi et al., 2023).

A second route to the same terminology comes from first-principles work on MoSe$_2$/WSe$_2$, which revealed two spin-orbit-split Rydberg series of interlayer excitons below the intralayer $2e\text{–}1h$0 excitons, with a significant binding energy on the order of $2e\text{–}1h$1 for the first excitons in the series. A plausible implication is that interlayer trions can also be built on excited interlayer excitonic orbitals, producing interlayer Rydberg trions in the stricter, excitonic-spectroscopy sense (Gillen et al., 2018).

2. Equilibrium interlayer trion liquids in electron–hole bilayers

The clearest realization of interlayer trions as equilibrium objects was reported in electrically gated two-dimensional van der Waals heterostructures with a genuine electron–hole bilayer geometry. Electrons reside in MoS$2e\text{–}1h$2 or MoSe$2e\text{–}1h$3, holes in WSe$2e\text{–}1h$4, and a monolayer or bilayer hBN tunneling barrier with $2e\text{–}1h$5 nm separates the layers. Because of type-II band alignment, gate voltage $2e\text{–}1h$6 and interlayer bias $2e\text{–}1h$7 tune the balance between interlayer attraction and charge imbalance, allowing continuous access to an exciton fluid, a trion fluid, an exciton–trion mixture, a trion–charge mixture, or an electron–hole plasma (Qi et al., 2023).

At commensurate density ratios, different few-body complexes are favored: $2e\text{–}1h$8 gives an interlayer exciton fluid, $2e\text{–}1h$9 favors positive interlayer trions $_2$0, and $_2$1 favors negative interlayer trions $_2$2. A simple zero-temperature counting model gives

$_2$3

which reproduces the experimentally inferred trion density maps. In the $_2$4 case, the two holes form a spin-singlet state with a spin gap of $_2$5 meV, and magneto-optical spectroscopy yields $_2$6 (Qi et al., 2023).

A related atomic-double-layer experiment on Coulomb-coupled MoSe$_2$7/WSe$_2$8 reached the degenerate quantum limit of a positive interlayer trion liquid. There the key commensurability condition is $_2$9, where holes in WSe$_2$0 are two times the electron density in MoSe$_2$1. The interlayer trion binding energy is about $_2$2, and the trion Fermi temperature is $_2$3, while transport was performed down to $_2$4. The charge gap extracted from $_2$5 decreases monotonically with density and vanishes near $_2$6, signaling a density-tuned transition to an electron–hole plasma (Nguyen et al., 2023).

3. Microscopic models, binding hierarchy, and Rydberg scaling

For indirect or interlayer trions in layered quasi-two-dimensional structures, the microscopic starting point is an effective-mass Hamiltonian with intralayer $_2$7 repulsion and interlayer attraction softened by the layer spacing $_2$8. In the bilayer-trion spectroscopy model for the positive interlayer trion, the hole-sector density of states was written as

$_2$9

with $_2$0, so that fitting the field-dependent oscillator strengths yields the trion occupancy and the spin gap $_2$1 (Qi et al., 2023).

A complementary few-body treatment of indirect trions in layered quasi-two-dimensional nanostructures used a configuration-space approach and derived analytical expressions for the trion binding energy as a function of interlayer distance. In that framework the ground-state trion binding energy is

$_2$2

with

$_2$3

The same analysis predicts that the trion binding energy is always greater than that of the biexciton, that there is no critical interlayer distance beyond which the trion abruptly disappears, and that typical layered structures with $_2$4 can support trion binding energies up to a few tens of meV (Bondarev et al., 2017).

The Rydberg connection enters through the excitonic parent states. In crystallographically aligned MoSe$_2$5/WSe$_2$6, first-principles GW–BSE calculations found spin-orbit-split interlayer exciton series $_2$7 and $_2$8 below the intralayer $_2$9 excitons. For AA′ stacking, the direct interlayer gap at $_2$0 is $_2$1, while $_2$2 appears at $_2$3 with a converged no-SOC binding energy $_2$4, and $_2$5 has a converged no-SOC binding energy $_2$6. This establishes the neutral interlayer Rydberg ladder from which charged interlayer Rydberg states can plausibly be constructed (Gillen et al., 2018).

4. Spectroscopy, higher-order complexes, and the polaron reinterpretation

In electron–hole bilayers, the hallmark of positive interlayer trion formation is the spin-singlet structure of the two holes. Magneto-reflectivity resolves a weaker intralayer trion peak $_2$7 and a higher-energy $_2$8 peak associated with a five-particle complex; $_2$9 is strongest at $\varepsilon_x \simeq 42 \pm 5\ \text{meV}$0 and decays symmetrically with increasing $\varepsilon_x \simeq 42 \pm 5\ \text{meV}$1, because the spin-singlet trion cannot be continuously polarized and is instead ionized once $\varepsilon_x \simeq 42 \pm 5\ \text{meV}$2 competes with $\varepsilon_x \simeq 42 \pm 5\ \text{meV}$3. The same platform supports higher-order complexes on top of exciton or trion fluids: tetrons, described as interlayer–intralayer hybrid biexcitons with $\varepsilon_x \simeq 42 \pm 5\ \text{meV}$4, and pentons, including a metastable positive-trion-based five-particle complex with $\varepsilon_x \simeq 42 \pm 5\ \text{meV}$5 relative to an interlayer trion far separated from an intralayer exciton (Qi et al., 2023).

A different spectroscopic setting produced an important correction to the simple “interlayer Rydberg trion” picture. In WSe$\varepsilon_x \simeq 42 \pm 5\ \text{meV}$6 sensor layers adjacent to MoSe$\varepsilon_x \simeq 42 \pm 5\ \text{meV}$7 or MoS$\varepsilon_x \simeq 42 \pm 5\ \text{meV}$8 sample layers, a redshifted resonance near the $\varepsilon_x \simeq 42 \pm 5\ \text{meV}$9 exciton had been interpreted as a bound state of a $\varepsilon_t \simeq 1.1 \pm 0.3\ \text{meV}$0 exciton and a remote carrier. Theoretical analysis showed instead that the $\varepsilon_t \simeq 1.1 \pm 0.3\ \text{meV}$1 polarizability is negative, $\varepsilon_t \simeq 1.1 \pm 0.3\ \text{meV}$2, while $\varepsilon_t \simeq 1.1 \pm 0.3\ \text{meV}$3; the $\varepsilon_t \simeq 1.1 \pm 0.3\ \text{meV}$4–carrier interaction is therefore repulsive at long range, and the three-body adiabatic potential connected to the $\varepsilon_t \simeq 1.1 \pm 0.3\ \text{meV}$5 threshold is too shallow to explain observed $\varepsilon_t \simeq 1.1 \pm 0.3\ \text{meV}$6 splittings. The visible resonance is instead a Rydberg attractive polaron, predominantly $\varepsilon_t \simeq 1.1 \pm 0.3\ \text{meV}$7 or interlayer exciton in character, that borrows oscillator strength from the bright $\varepsilon_t \simeq 1.1 \pm 0.3\ \text{meV}$8 state (Christianen et al., 7 Dec 2025).

The spacing dependence of the redshifted resonance reinforces that reinterpretation. For example, the stable $\varepsilon_t \simeq 1.1 \pm 0.3\ \text{meV}$9 values were reported as $_2$0 for a $_2$1 nm spacer, $_2$2 for $_2$3 nm, $_2$4 for $_2$5 nm, and $_2$6 for $_2$7 nm. In the structures studied there and in most current TMD heterostructure experiments, the experimentally visible “Rydberg” resonance is therefore better understood as a many-body polaron resonance, not a pure interlayer three-body Rydberg trion (Christianen et al., 7 Dec 2025).

5. Moiré-trapped, intervalley, and quadrupolar interlayer trions

Moiré heterobilayers introduce a different regime, in which interlayer excitons and trions are localized by periodic trapping potentials rather than forming an extended bilayer fluid. In near-$_2$8 MoSe$_2$9/WSe$_2$0 moiré heterobilayers, the interlayer complex spectrum resolves three photoluminescence bands: trions, neutral interlayer excitons, and bi-excitons. The trion–exciton splitting is $_2$1, the exciton–bi-exciton splitting is $_2$2, and no Rydberg trion series is resolved. A central result is the absence of optical generation of trions: trion PL scales with electrostatically doped electrons, not with optically generated carriers, which the authors attribute to highly localized, near sub-nm confinement of trapped species in moiré potentials (Ray et al., 2023).

A related optical read-out experiment on a $_2$3-type MoSe$_2$4/WSe$_2$5 heterobilayer showed that neutral trapped interlayer excitons convert uniformly into charged interlayer excitons with a binding energy of $_2$6 on initial doping. Further filling generates a Coulomb staircase, namely stepwise changes in IX trion emission energy due to Coulomb interactions with carriers at nearest-neighbour moiré sites, with typical energy jumps of $_2$7 and an inferred moiré period $_2$8 (Baek et al., 2021).

Charge-tunable $_2$9-WSe$2e\text{–}1h$00/MoSe$2e\text{–}1h$01 heterobilayers also resolve several localized negative interlayer trion species with contrasting spin–valley configurations. The main lines were assigned to an intervalley spin-triplet trion, an intravalley spin-triplet trion, and an intervalley spin-singlet trion, with measured $2e\text{–}1h$02-factors $2e\text{–}1h$03, $2e\text{–}1h$04, and $2e\text{–}1h$05, respectively. In twisted MoSe$2e\text{–}1h$06 homobilayers, a distinct room-temperature route to interlayer-related trions appears through intervalley hybrid trions involving the $2e\text{–}1h$07- and $2e\text{–}1h$08-points in the conduction band and the $2e\text{–}1h$09-point in the valence band; the gate dependence is strong for $2e\text{–}1h$10 and weak for $2e\text{–}1h$11, consistent with twist-angle-dependent interlayer hybridization at the $2e\text{–}1h$12 valley (Brotons-Gisbert et al., 2021, Rosa et al., 2024).

A more recent extension uses a bichromatic moiré superlattice in an asymmetric WSe$2e\text{–}1h$13/WS$2e\text{–}1h$14/WSe$2e\text{–}1h$15 heterotrilayer. There the system hosts fermionic quadrupolar moiré trions—interlayer excitons bound to an opposite-layer hole—with vanishing dipole moments. The low-energy and high-energy excitonic orbitals are separated by $2e\text{–}1h$16, and an out-of-plane electric field reshapes the moiré landscape, driving a transition from interlayer to intralayer Mott states while toggling dipolar and quadrupolar character (Chen et al., 18 Sep 2025).

6. Correlated phases, dynamics, and broader significance

At commensurate $2e\text{–}1h$17 density imbalance, theory predicts a broader family of strong-coupling phases than a simple trion gas. Three length scales—interparticle distance $2e\text{–}1h$18, layer separation $2e\text{–}1h$19, and effective Bohr radius $2e\text{–}1h$20—control the competition between kinetic energy, intralayer repulsion, and interlayer attraction. Depending on parameter regime, the predicted phases include quantum crystals of electrons, excitons, and trions, as well as an excitonic supersolid featuring electron crystallization and exciton superfluidity simultaneously (Dai et al., 2023).

The experimentally realized bilayer trion fluids already display several of these strong-coupling ingredients. Interlayer trions are charged and heavy, their mutual Coulomb repulsion can dominate over kinetic energy, and the reported phase diagrams explicitly motivate trion Wigner crystallization and trion-mediated topological superconductivity. In this sense, the Rydberg analogy is not only about weak internal binding; it also concerns strong, long-range interactions between composite particles in a tunable two-dimensional environment (Qi et al., 2023).

Time-resolved measurements on WSe$2e\text{–}1h$21/twisted-bilayer-graphene heterostructures extend the same conceptual shift from trions to many-body polarons into a dynamical regime. After pump injection of Rydberg excitons, the lowest moiré Rydberg branch undergoes a time-dependent redshift that is negligible at $2e\text{–}1h$22 but reaches $2e\text{–}1h$23 for $2e\text{–}1h$24 and $2e\text{–}1h$25 or larger for $2e\text{–}1h$26. The corresponding relaxation rate grows to $2e\text{–}1h$27 for large hole doping and $2e\text{–}1h$28 for large electron doping, while the recovery time increases from $2e\text{–}1h$29 near charge neutrality to $2e\text{–}1h$30 at high hole density. In the low-density limit, these interlayer Rydberg exciton Fermi polarons connect continuously to trion-like states (Arsenault et al., 16 Jun 2025).

Taken together, these results suggest that “interlayer Rydberg trions” do not designate a single microscopic object. The term spans weakly bound equilibrium interlayer trions in electron–hole bilayers, moiré-trapped charged interlayer excitons with multi-orbital and spin–valley structure, and Rydberg-exciton-related resonances whose proper description can cross over from a discrete three-body bound state to a hybridized exciton–polaron. The unifying features are spatial separation across layers, electrically tunable Coulomb coupling, and an energy hierarchy in which binding, screening, hybridization, and collective correlations remain of comparable importance (Qi et al., 2023, Christianen et al., 7 Dec 2025, Dai et al., 2023).