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Shuichi Asada, Keisuke Shinokita, [Kenji Watanabe](https://orcid.org/0000-0003-3701-8119), [Takashi Taniguchi](https://orcid.org/0000-0002-1467-3105), Kazunari Matsuda

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[Nonlinear photovoltaic effects in monolayer semiconductor and layered magnetic material hetero-interface with P- and T-symmetry broken system](https://mdr.nims.go.jp/datasets/b1276538-d0dc-4305-b123-862163037a46)

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Nonlinear photovoltaic effects in monolayer semiconductor and layered magnetic material hetero-interface with P- and T-symmetry broken systemArticle https://doi.org/10.1038/s41467-025-58918-9Nonlinear photovoltaic effects in monolayersemiconductor and layered magneticmaterial hetero-interface with P- andT-symmetry broken systemShuichi Asada1, Keisuke Shinokita 1, Kenji Watanabe 2, Takashi Taniguchi 3 &Kazunari Matsuda 1Stacking two non-polar materials with different inversion- and rotational-symmetries shows unique nonlinear photovoltaic properties, with potentialapplications such as in next generation solar-cells. These nonlinear photo-current properties could be further extended with broken time reversal sym-metry present in magnetic materials, however, the combination of timereversal and rotation symmetry breaking has not been fully explored. Herein,we investigate the nonlinear photovoltaic responses in van der Waals hetero-structure compromising of monolayer semiconductor and layered magneticmaterial, MoS2/CrPS4; a system with broken P- and T-symmetry. We clearlyobserve thefinite spontaneous photocurrent as shift current at the interface ofthe MoS2/CrPS4 heterostructure. Moreover, we demonstrate that the sponta-neous photocurrent drastically changes according to the magnetic phases ofCrPS4. The magnetic phase dependent spontaneous nonlinear photocurrentprovides a platform for studying nonlinear photoresponses in systems withbroken P- and T-symmetry, and the potential development of magnetic con-trollable photovoltaic devices.Recently, the introduction of shift current concepts from topologicalphysics drastically extend the possibilities for photovoltaic devicesbecause of their unconventional spontaneous photocurrentproperties1–4. The shift current as one of the bulk photovoltaic effectsare themostpromising photovoltaic responses to be able to overcomethe Shockley–Queisser limit in the conventional p-n junction photo-voltaic devices5–8. These anomalous photovoltaic responses includingextremely large open-circuit voltage, not limited by band-gap energy,and robust photocurrent to defects and impurities of materials, havebeen observed in the polar bulk materials9–13. The shift current couldbe explained as topological photocurrent depending on Berry con-nection, which is a vector in real space indicating the information ofcenter-of gravity position of electrons14,15. In the crystal with brokenspatial inversion (P-) symmetry, the imbalance electron “shift” due tooptical interband transitions before and after photoexcitation isoccurred, which then generates the spontaneous photocurrent underzero-bias conditions as shift current. In addition to the shift current,the nonlinear topological photoresponses also induce the injectioncurrent, which is caused by difference of group velocity and imbalancephotoexcitation with circular polarized light in k-space16–18. Since theshift current and injection current are induced by the linear- andcircular-photogalvanic effects (LPGE and CPGE) of linearly and circu-larly polarized light, respectively, their effects are generally observedseparately. However, in time-reversal (T-) symmetry broken crystalsReceived: 1 May 2024Accepted: 3 April 2025Check for updates1Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan. 2Research Center for Functional Materials, National Institute for Materials Science,1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan. 3International Center for Materials Nanoarchitectonics, National Institute for Materials Science, 1-1 Namiki,Tsukuba, Ibaraki 305-0044, Japan. e-mail: matsuda@iae.kyoto-u.ac.jpNature Communications |         (2025) 16:4827 11234567890():,;1234567890():,;http://orcid.org/0000-0002-7752-3251http://orcid.org/0000-0002-7752-3251http://orcid.org/0000-0002-7752-3251http://orcid.org/0000-0002-7752-3251http://orcid.org/0000-0002-7752-3251http://orcid.org/0000-0003-3701-8119http://orcid.org/0000-0003-3701-8119http://orcid.org/0000-0003-3701-8119http://orcid.org/0000-0003-3701-8119http://orcid.org/0000-0003-3701-8119http://orcid.org/0000-0002-1467-3105http://orcid.org/0000-0002-1467-3105http://orcid.org/0000-0002-1467-3105http://orcid.org/0000-0002-1467-3105http://orcid.org/0000-0002-1467-3105http://orcid.org/0000-0002-3990-8484http://orcid.org/0000-0002-3990-8484http://orcid.org/0000-0002-3990-8484http://orcid.org/0000-0002-3990-8484http://orcid.org/0000-0002-3990-8484http://crossmark.crossref.org/dialog/?doi=10.1038/s41467-025-58918-9&domain=pdfhttp://crossmark.crossref.org/dialog/?doi=10.1038/s41467-025-58918-9&domain=pdfhttp://crossmark.crossref.org/dialog/?doi=10.1038/s41467-025-58918-9&domain=pdfhttp://crossmark.crossref.org/dialog/?doi=10.1038/s41467-025-58918-9&domain=pdfmailto:matsuda@iae.kyoto-u.ac.jpwww.nature.com/naturecommunicationssuch as some layered magnetic materials, each spin band is lifted byspin polarization and shows an imbalanced band structure inmomentum space. The electron is photoexcited unevenly in terms ofmomentum, and the group velocity of the electron is not perfectlycanceled,whichwould induce a linear injection current in systemswithbroken T-symmetry19–22. The shift current is also induced by the CPGEafter the magnetic transition. These magnetic PGEs have odd parityunder magnetization changes; thus, they are not observed in non-magnetic materials where T-symmetry is preserved23.The emerging two-dimensional (2D) materials, including semi-conducting transition metal dichalcogenides have opened the newresearchfields in the fundamental science andpotential applications invarious electronic and optical applications24–26. The artificial van derWaals (vdW) heterostructures fabricated by stacking 2Dmaterials leadto induce the emerging periodicity of crystal structures such as moirésuperlattice27–32 and provide us the new pathways to control the P-symmetry at their heterointerfaces. Recently, it has been reported thenonlinear photocurrent arising from shift current in the artificially P-symmetry breaking vdW heterointerface by stacking three-fold sym-metryMoS2 and two-fold symmetryblackphosphrous33.Moreover, theartificial symmetry breaking would extend the exploration for highefficiency shift current photovoltaic devices34–36, however, no pro-mising candidates have been shown37. Accordingly, it is crucial toexperimentally investigate the shift current and injection currentdepending on Berry connection and Berry curvature in the novelinterface of vdW heterostructure with the systems with broken P- andT-symmetry. The understanding of nonlinear photocurrent responsesin the vdW heterostructure with the system with broken P- and T-symmetry would provide the ground breaking importance for funda-mental physics and applications for emerging photovoltaics.In this study, we demonstrated the nonlinear photoresponses inmonolayer semiconductor and layered magnetic materials vdW het-erostructure with the systemwith broken P- and T-symmetry. The shiftcurrent along the direction of parallel to P-symmetrybroken axis at theinterface ofMoS2/CrPS4 vdWheterostructure has been experimentallyobserved above 40K. Moreover, we demonstrate the switchablespontaneous photocurrent arising from themagnetic phase transitionof CrPS4 in vdW heterostructure depending on the temperature andexternal magnetic fields. The detail physical mechanism of anomalousspontaneous photocurrents in the vdW heterostructure with the sys-tem with broken P- and T-symmetry will be discussed.ResultsFigure 1a shows a schematic of photocurrent measurement of mono-layer (1L)-MoS2 and multi-layers CrPS4 vdW heterostructure device.The rotational and P-symmetry by stacking of three-fold symmetryMoS2 and two-fold symmetry CrPS4 are diminished, and reduced attheir interface38–40, and only one-mirror plane ismaintained at the vdWinterface, as shown in the inset of Fig. 1a. The (x, y, z) axes are definedfor the crystal structure as shown in the inset of Fig. 1a. Figure 1b showsthe optical image of monolayer MoS2 and multi-layers CrPS4 vdWheterostructure device. The monolayer MoS2 and multi-layers CrPS4were mechanically exfoliated from bulk single crystals, respectively,and then themonolayerMoS2was stackedonmulti-layersCrPS4 bydrytransfer method (see the “Methods” section). The twist-angle betweenMoS2 and CrPS4 was controlled to match each mirror planes withjudging from each characteristic cleaved edge angle of 67.5° and 60°for multi-layers CrPS4 and monolayer MoS2, respectively41–43. Theheterostructure fabrication was confirmed from photoluminescencespectrum as shown in Fig. 1c.Figure 1d shows the current–voltage (I–V) characteristics mea-sured along the x-axis of MoS2/CrPS4 vdW heterostructure device,under dark (black) and illumination of linearly polarized light of532nm (red) at room temperature. The I‒V characteristics under darkconditions show simple linearbehavior in the currentwhen the appliedbias voltage is not zero. The significant finite value of spontaneousedbcaMoS�CrPS4E4E2E1E320 μmP1L-MoS�CrPS4PxyzMo SCr PFig. 1 | Schematic of 1L-transition metal dichalocogenide/CrPS4 vdW hetero-structure device. a Schematic of photocurrent measurement of 1L-MoS2/CrPS4vdW heterostructure device. The inset shows schematic of in-plane crystalstructure of 1L-MoS2/CrPS4 vdW heterostructure. The green and red dotted linesshow the axis of inversion symmetry MoS2 and CrPS4, respectively. In the het-erointerface, the inversion symmetry is reduced to maintain in only one mirrorplane and rotational symmetry is canceled. Consequently, the spontaneouspolarization indicated by the red arrows with broken P-symmetry are induced,according to the overlapped mirror plane. bOptical image of 1L-MoS2/CrPS4 vdWheterostructure device. The scale bar of 20μm is shown in the images. The 1L-MoS2 was stacked onmulti-layer CrPS4, and four-electrodes were fabricated alongto parallel and perpendicular to expected polarization direction.c Photoluminescence (PL) spectrum of 1L-MoS2/CrPS4 vdW heterostructure. ThePL peaks at 1.92, and 1.38 eV correspond to the emissions from 1L-MoS2, andCrPS4, respectively. d I–V curve of 1L-MoS2/CrPS4 vdW heterostructure deviceunder dark and laser illumination of 532 nm conditions. e I–V curve of 1L-WSe2/CrPS4 vdW heterostructure device under dark and laser illumination of 532 nmconditions.Article https://doi.org/10.1038/s41467-025-58918-9Nature Communications |         (2025) 16:4827 2www.nature.com/naturecommunicationsphotocurrent at zero-bias voltage is clearly observed under laser illu-mination, which is in contrast to no spontaneous photocurrent, i.e. thezero-current at zero-bias voltage under dark condition. Moreover, thespontaneous photocurrent under light illumination is also observed inthe WSe2/CrPS4 vdW heterostructure based on different monolayersemiconductor, as shown in Fig. 1e (see details in Fig. S1). Spontaneousphotovoltaic effects were not observed in the devices with only theMoS2 monolayer or bulk CrPS4 (see Figs. S2 and S3). These resultsstrongly imply that the experimentally observed spontaneous photo-current is a universal behavior in the monolayer semiconductor tran-sition metal dichalocodenide/CrPS4 vdW heterostructure device.Figure 2a shows the optical image of MoS2/CrPS4 vdW hetero-structure device with four electrodes (E1–E4) to investigate the direc-tion of nonlinear spontaneous photocurrent, where the fourelectrodes indicated by red dashed lines are fabricated in the center ofMoS2/CrPS4 heterostructure region. The photocurrent measurementsusing E1 and E2 (E3 and E4) correspond to photocurrent generationalong the x- and y-axes, respectively. It has been well known that theshift current strongly depends on spontaneous polarizationdirection33,44. The significant spontaneous photocurrent at zero-biasvoltage is clearly observed along to the x-axis and mirror plane, whileno spontaneous photocurrent is observed along to the y-axis evenunder the same photoexcitation conditions, as shown in Fig. 2b.Figure 2c shows the I–V characteristics with various laser inten-sities from 2 to 360μW measured between E1 and E2 electrodes. Thespontaneous photocurrent at zero-bias voltage increases withincreasing the laser intensities. The laser power dependence of spon-taneous photocurrent is plotted in Fig. 2d. The spontaneous photo-current linearly increases as a function of laser power in the weakpower conditions below 5μW, while the spontaneous photocurrentgradually saturates in the high power conditions. The behavior ofnonlinear power dependence of spontaneous photocurrent is muchdifferent from the linear power dependence from photovoltaicresponses of p–n junction and Schottky barrier45–47. The possiblemechanism for the nonlinear spontaneous photocurrent is one of thesecond-order nonlinear optical responses, the shift current, which iscaused in the system with broken P-symmetry arising from the shift ofcenter of gravity electron position in real space before and afterphotoexcitation14. The nonlinear shift current Jshift as a function ofexcitation power P is described as follows:Jshift = S0 � PffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiS1 � P + S2p ð1Þwhere S0, S1, and S2 are coefficients, which contribute to the shiftcurrent4,48. When P is enough small, S2 becomes dominant comparewith S1, and Jshift shows linear dependence as a function of P, as shownin the green dotted line in Fig. 2d. Moreover, S1 becomes dominantwith increasing P and shows P1/2 power dependence, as shown in thered dotted line in Fig. 2d. The experimental result of spontaneousphotocurrent as a function of excitation power is well reproduced bythe calculated result using Eq. (1). This nonlinear photocurrent ismuchcontradict to the linear photocurrent arising from Schottky barrier49,which implies that the experimentally observed spontaneous photo-current comes from the shift current.Figure 2e shows the spontaneous photocurrentmapping inMoS2/CrPS4 vdW heterostructure between E1 and E2 under laser light illu-mination of 532 nm and an excitation power of 600μW. The positiveabc edfISC∝PISC∝P1/2E1-E2E1E2E3E4CrPS4MoS2E1 E2E3E4P5 μmFig. 2 | Photovoltaic properties of 1L-MoS2/CrPS4 vdW heterostructure devicein roomtemperature. aOptical imageof 1L-MoS2/CrPS4 vdWheterostructurewithfour electrodes configurations. The electrodes are highlighted in red dotted lines,and each electrode is assigned as E1–E4 to clarifymeasurement direction. The scalebar of 5 μm is shown in the images. Hereinafter, measurement results withoutannotations indicate the results between the E1 and E2 along to predicted polar-ization direction. b I–V characteristics of 1L-MoS2/CrPS4 vdW heterostructureunder the laser illumination of 532 nm, which were measured by different currentdetection configurations with parallel (E1 and E2) and perpendicular (E3-E4) toexpected polarization. c I–V characteristics of 1L-MoS2/CrPS4 vdW heterostructurewith various excitation powers. d Excitation laser power dependence of sponta-neous photocurrent of 1L-MoS2/CrPS4 vdW heterostructure. In the low powerregion, the spontaneous photocurrent is proportional to the laser power, whereasthe square-root dependence of the photocurrent is observed in the high powerregion. e Photocurrent mapping measured between the E1 and E2 electrodes,indicated by the dotted lines. f Polar plot of spontaneous photocurrent with linearpolarized light along to E1 and E2 direction. 0° and 180° correspond to E1 and E2electrodes, respectively.Article https://doi.org/10.1038/s41467-025-58918-9Nature Communications |         (2025) 16:4827 3www.nature.com/naturecommunicationsand negative photocurrent signals around each electrode due toSchottky barrier internal voltage between heterostructure and metalelectrodes are clearly observed in the photocurrent mapping. Moreimportantly, the large spontaneous photocurrent is observed in thecenter of heterostructure region far from electrodes (see Fig. S4), andthe spontaneous photocurrent in the center strongly depends on themeasurement direction (see Fig. S5). These results strongly imply thatthe experimentally observed spontaneous photocurrent in the het-erostructure region comes from intrinsic photovoltaic properties inthe monolayer semiconductor/CrPS4 heterointerface.Figure 2f shows the laser polarization angle dependence ofspontaneous photocurrent in MoS2/CrPS4 vdW heterostructure (alsosee in Fig. S6), in which the linearly polarization angle of incident laserlight is defined as relative angle from the mirror-plane (x-axis) of het-erointerface. Thepolar plotof spontaneousphotocurrent as a functionof polarization angle showsweakly anisotropic responsewith two-foldsymmetry, along with symmetric axis of parallel to mirror-plane inMoS2/CrPS4 vdW heterointerface. According to the theoretical calcu-lation, the polar plot of the spontaneous bulk photovoltaic effect withonly monolayer MoS2 with C3 symmetry is expected to show threefoldsymmetry and both positive and negative signals33,50; however, thepolar plot of the spontaneous photocurrent of the MoS2/CrPS4 vdWheterostructure shows twofold symmetry along the spontaneouspolarization direction and consistently positive signals, as shown inFig. 2f. Thus, the experimentally observed spontaneous photocurrentis caused by the shift current induced by the broken P-symmetry at theMoS2/CrPS4 vdW heterointerface. However, these results are char-acteristic of bulk photovoltaics, which may not occur due to the shiftcurrent alone. In addition to the shift current, the ballistic currentmight also be considered a bulk photovoltaic effect that occurs underlinearly polarized light excitation51,52. However, the major differencebetween the shift current and ballistic current is the response to cir-cularly polarized light53,54. As shown in Fig. S7, the spontaneous pho-tocurrent in the MoS2/CrPS4 heterostructure device disappears undercircularly polarized light (CPL), suggesting that the effect of the bal-listic current is negligible. The measured spontaneous current underCPL in Fig. S7 comes from a nonmagnetic injection current, forexample, from a ballistic current induced by CPL. The experimentallyobserved injection current is a novel result that has not been reportedfor artificial vdW heterointerfaces, which provides new insights intothe bulk photovoltaic effect at artificial vdW heterointerfaces.The nonlinear spontaneous photocurrent induced by the break-ing of T-symmetry in addition to P-symmetry is investigated in theMoS2/CrPS4 vdW heterostructure, because the vdW heterointerface isformed between themonolayer semiconductor andmagneticmaterialof CrPS4. Figure 3a shows the temperature dependenceof I–V curves inthe MoS2/CrPS4 vdW heterostructure under the illumination of laserwith a wavelength of 532 nm and power of 600μW. With decreasingtemperature from300 to 40K, the gradient of I–V curve decreases andopen-circuit voltage increases. The fill factor is ~0.25 independent oftemperature, as shown in Fig. S8, due to the linear I‒V characteristicsofthebulk photovoltaic effect. The effective series resistances in the vdWheterostructure are evaluated from the gradient of the linear I‒Vcurves. The lower panel of Fig. 3b shows the effective series resistance(blue dot and line) and open-circuit voltage (green dot and line) ofMoS2/CrPS4 vdW heterostructure as a function of temperature. Theeffective series resistance increases with decreasing temperature until40K, which corresponds to the temperature dependence of resistivityin monolayer MoS255,56. Moreover, the open-circuit voltage alsoincreases with decreasing temperature above 40K.Figure 3a shows the drastically change of I–V curve withdecreasing temperature below 40K. The spontaneous photocurrentshows almost constant values above 40K as shown in Fig. 3a, while themost significant change in the temperature dependence of I–V curve isdrastically decrease of spontaneous photocurrent below ∼40K. Fig-ure 3b shows the plot of spontaneous photocurrent as a function oftemperature. The critical decrease of spontaneous photocurrent iscelery observed below 40K. Moreover, the trend of open-circuit vol-tage also changes below the critical temperature of 40K, as shown inthe lower panel of Fig. 3b.The critical temperature of 40K well corresponds to the magnetictransition temperature from paramagnetic to anti-ferromagnetic (AFM)phase of CrPS4 as Neel temperature (TN = 38K)57–60. It is expected thatthe shift current as physical origin of spontaneous photocurrent showstemperature independentbehavior, because it comes fromthecenter ofgravity position shift of excited electrons in the photoexcitation pro-cess, which is not to be affected by the defect and atomic registry61,62.However, the spontaneous photocurrent significantly decreases belowNeel temperature of 40K in CrPS4, which strongly implies the physicalmechanism of nonlinear spontaneous photocurrent in addition to theshift current in the system with broken T-symmetry and P-symmetry ofMoS2/CrPS4 heterointerface at low temperature.a b20 μmCrPS4MoS2x4Fig. 3 | Temperature dependence of photovoltaic properties of MoS2/CrPS4vdWheterostructure device. a Temperature dependence of I–V characteristics ofMoS2/CrPS4 vdW heterostructure under the light illumination from 10 to 200K.b Spontaneous photocurrent at zero-bias voltage as a function of temperature inthe upper panel. The inset shows the temperature dependence of spontaneousphotocurrent, and optical image in another MoS2/CrPS4 vdW heterostructuredevice. The open-circuit voltage, as indicated by green dots and lines in the lowerpanel and effective series resistance calculated by the gradient of I–V curve, asindicated by the blue dots and line in lower panel. The black dotted line at 40Kindicates Neel temperature of CrPS4.Article https://doi.org/10.1038/s41467-025-58918-9Nature Communications |         (2025) 16:4827 4www.nature.com/naturecommunicationsWe will discuss the anomalous and critical change of sponta-neous photocurrent below 40K. The shift current is described as theproduct of terms of optical transition probability and shift vector14.Noted that the optical transition probability measured by the dif-ferential reflectance spectra in the vdW heterostructure does notchange below 40K of Neel temperature in themulti-layers CrPS4 (seein Fig. S9), which suggests that the factor of optical transitionprobability is not the main physical reason of the critical change ofspontaneous photocurrent. The magnetic phase change of CrPS4 atthe heterointerface would affect the shift vector, however, it hasrevealed that the shift vector itself does not depend on the T-symmetry63. The magnetic lattice distortion accompanied by mag-netic phase transition would also cause the possibility of change ofshift-vector64, however, we could not observe any clear changes ofRaman spectrum below 40K as shown in Fig. S10. Moreover, thetemperature dependence of lattice constant in bulk CrPS4, especially,x-axis along to expected polarization direction shows continuouslychange from 300 to 10K straddling 40K according to the previousresult39 (see Fig. S11). Noted that the change of lattice constant issmall value of only about 0.03% between 40 and 10K. These aremuch contradict to the experimental results of constant values ofspontaneous photocurrent from 300 to 40K and critical changebelow 40K, as shown Fig. 3a. Moreover, the spontaneous photo-current also shows different behavior of clear enhancement belowNeel temperature in another device of MoS2/CrPS4 vdW hetero-structure, as shown in in the inset of Figs. 3b and S12. Theseexperimental results strongly suggest that the change of opticaltransition probability and shift vector induced by magnetic latticedistortion cannot explain the reversible change of shift currentdepending on the device. Thus, the experimentally observed sig-nificant and critical change of spontaneous photocurrent below 40Kdoes not come from the change of shift current.As described above, the shift current does not be affected by T-symmetry of the system, although, the experimental results of spon-taneous photocurrent in MoS2/CrPS4 vdW heterostructure stronglydepend on the magnetic state of CrPS4 layer, which implies additionalnonlinear photocurrent mechanism in the system with broken P- andT-symmetry. The recent theoretical studies of nonlinear photocurrentpredict the generation ofmagnetic injection current due to imbalancephotoexcitation of electrons in momentum space in layered magneticmaterials such as CrPS4 with the system with broken P- and T-symmetry19,22,23. The spontaneous photocurrent in AFM CrPS4 belowNeel temperature (TN∼ 40K) might be affected by the generation ofmagnetic injection current. As shown in Fig. S13, bulk CrPS4 does nothave a spontaneous photocurrent even below the Neel temperature,which suggests that the magnetic injection current is induced by asystem with broken P-symmetry, such as the heterointerface of MoS2and CrPS4. The experimental result of the critical decrease in thespontaneous photocurrent shown in Fig. 3a (also shown in Fig. S12)comes from the generation of a magnetic injection current with anegative sign superimposed on the temperature-independent shiftcurrent, which will be discussed later. The generation of a magneticinjection current and shift current due to a decrease in temperatureand a change in the magnetic order state are shown in Table S1.In order to experimentally investigate the relationship betweenspontaneous photocurrent and magnetic states of CrPS4, we mea-sured external magnetic field dependence of photocurrent in thevdW heterointerface below 40K. Figure 4a, and b show the I–Vcurves in MoS2/CrPS4 vdW heterostructure with applying out ofplane magnetic fields at 10 and 35 K below Neel temperature. Therelationship between the magnetic state of CrPS4 at each tempera-ture and the out-of-plane magnetic field is shown in Fig. S14. The I–Vcurve changes and the spontaneous photocurrent increases with thesweep of out of plane magnetic field from 0 to 3 T (from 0 to −3 T) at10 K, as shown in Fig. 4a. Figure 4c shows the spontaneous photo-current as a function of out of plane magnetic field at 10 K. Figure 4cand d show the results under the sweeping of magnetic field from0T. The effect of hysteresis on the spontaneous photocurrent isshown in Fig. S15. The spontaneous photocurrent quickly increases atthe boundaries of ±2 T, which is caused by themagnetic field inducedphase transition from A-type AFM with out-of-plane ferromagneticordered spins to canted-antiferromagnetic state with ordered cantedspins within a layer (A-AFM) and canted anti-ferromagnetic orderedspins (CAFM) of CrPS460. The experimental result of increase ofspontaneous photocurrent in Fig. 4c comes from decrease of nega-tive sign magnetic injection current depending on the magneticphase of CrPS4 superimposed to shift current triggered by phasetransition from A-AFM to CAFM of CrPS4 by external out of planeabCAFM CAFMA-AFM CAFMFM FMdcFig. 4 | Externalmagneticfielddependenceofphotovoltaic properties ofMoS2/CrPS4 vdW heterostructure device. a and b I–V characteristics of MoS2/CrPS4vdWheterostructurewith external out of planemagneticfield from −7 to 7 T at 10K(a) and 35K (b). c and d External magnetic field dependence of spontaneousphotocurrent is represented by red dots at 10 K (c) and 35K (d). Each coloredregion shows the magnetic state of CrPS4, ferromagnetic (FM, blue), canted anti-ferromagnetic (CAFM, green) and A-type anti-ferromagnetic (A-AFM, red),respectively60. The black dotted line in d shows the value of shift current above40K. The schematic of crystal and spin structures of 1L-MoS2/CrPS4 vdW hetero-structure are shown in the figures.Article https://doi.org/10.1038/s41467-025-58918-9Nature Communications |         (2025) 16:4827 5www.nature.com/naturecommunicationsmagnetic field in the vdW heterostructure, because the value ofmagnetic injection current in A-AFM state is larger than that in CAFMstate. As shown in Fig. S16, electrical resistance R is constant withrespect to the external magnetic field; thus, the change in sponta-neous photocurrent clearly does not result from the change in carriermobility.The I–V curve changes and the spontaneous photocurrent increa-ses with the sweep of out of plane magnetic field from 0 to 7T (from 0to −7T) at 35K, as shown in Fig. 4b. Figure 4d shows the magnetic fielddependence of spontaneous photocurrent at 35K near Neel tempera-ture. The spontaneous photocurrent increases with the sweep of out ofplane magnetic field from 3 to 7T (from −3 to −7T) at 35K. The spon-taneous photocurrent also quickly increases at the boundaries of ±4T,which is caused by the magnetic field induced phase transition fromCAFM to ferromagnetic (FM) ordered state of CrPS4. Above externalmagnetic field of ±4T, the values of spontaneous photocurrent reach toalmost same value without magnetic field above Neel temperature of40K, which is indicated by the dotted line in Fig. 4d. The stepwiseincrease of spontaneous photocurrent in Fig. 4d comes from the dis-appearance of magnetic injection current and residual shift current inthe spontaneous photocurrent bymagnetic phase transition fromCAFMto FM of CrPS4 by external magnetic field.The sign of magnetic injection current is determined by the up-and down-spin of top layer in the AFM state, and reversed AFM19,22,23.The two-types of heterointerface of MoS2/CrPS4 vdW heterointerfaceare possible in AFM, and reversed-AFM of CrPS4 below Neel tem-perature (TN). The experimental results of critical increase, anddecrease of spontaneous photocurrent induced by A-AFM transition,as shown in Figs. 3a, and S12 are well consistent with the cases of vdWheterointerface with AFM, and reversed-AFM of CrPS4, respectively.Themagnetic state switchable spontaneous photocurrent phenomenadescribed above are understood by the change of magnetic injectioncurrent superimposed to shift current in vdW heterointerface. Theseresults strongly imply the experimental observation of characteristicphenomena of nonlinear spontaneous photocurrent in vdW hetero-structure with the system with broken P- and T- symmetry.DiscussionWe studied nonlinear photocurrent responses of MoS2/CrPS4 vdWheterostructure with the system with broken P- and T-symmetry. Thefinite spontaneous photocurrent arising from shift current along theparallel axis to mirror plane at the interface of MoS2/CrPS4 has beenobserved. Moreover, we demonstrated that the spontaneous photo-current drastically changes below Neel temperature of A-type AFMCrPS4 in MoS2/CrPS4 heterostructure. The spontaneous photocurrentalso changes depending on external magnetic field below the Neeltemperature, accompanied by field induced magnetic phase transi-tion. The critical suppression (enhancement) of spontaneous photo-current below Neel temperature is caused by competition of the shiftcurrent and sign of magnetic injection current in MoS2/CrPS4 vdWheterointerface. Our results of magnetic switchable photovoltaicresponses demonstrated here provide the new aspects on the non-linear photovoltaic effects in P- and T-symmetry breaking vdW het-erointerface, and new strategy for next-generation solar cells.MethodsSample preparationMonolayer (1L) MoS2 and thick multi-layers CrPS4 were prepared on270-nm-thick SiO2 on Si substrates by mechanical exfoliation fromtheir respective bulk single crystals. The thickness of MoS2 wasdetermined from the optical contrast and photoluminescence (PL)spectra. The MoS2/CrPS4 heterostructure was fabricated by apolydimethylsiloxane (PDMS)-based viscoelastic transfer techniqueusing poly-methyl methacrylate (PMMA) stamp. The PMMA layerwas washed away by immersing the sample in an acetone solution.The microelectrode pattern was fabricated by photolithographymethod, and Bi/Au electrodes were thereafter fabricated by thermalevaporation method. The stacking angle θ defined by therelative angle between zigzag direction of 1L-MoSe2 and a-axis ofCrPS4 in the heterostructure was evaluated to be 0 ± 1° by the edgeangle in optical image38,39,65. The correspondence betweenthe characteristic edge angles and the crystal structure wasconfirmed by polarized Raman scattering and SHG measurements(Figs. S17 and S1)8,66,67.Photocurrent measurementA linearly polarized green laser (532 nm)wasused as an excitation lightsource for the photocurrent measurements. The I–V characteristics ofthe devicewasmeasured in the shield box (Keithley, 8101-PIV) at roomtemperature and in the cryostat (Janis Research, ST-500-UC) for thetemperature variable measurements, respectively. The micro-Ramansetup (Nanophoton, Ramantouch) was used for the measurement ofPL, Raman scattering, and differential reflectance spectra. The source-meter (Keithley, 2636B) was used for applying the bias voltage andmeasure of current.Magnetic photocurrent measurementsA linearlypolarizedgreen laser (520 nm)was used as an excitation lightsource for I–V characteristics measurement under out of plane mag-netic field. The device was cooled by the He-flow cryostat (JanisResearch, ST-500), and the magnetic field was generated by thesuperconductive magnet (Cryogenic, mCFM). The sourcemeter(Keithley, 2614B)was used for applying the bias voltage andmeasuringthe current under magnetic fields.Data availabilityData presented in this paper and the supplementary materials areavailable from the corresponding author upon request.References1. Nakamura, M. et al. Shift current photovoltaic effect in a ferro-electric charge-transfer complex. Nat. Commun. 8, 281 (2017).2. Ma, J. et al. Nonlinear photoresponse of type-II Weyl semimetals.Nat. Mater. 18, 476–481 (2019).3. Cook, A. M., M Fregoso, B., de Juan, F., Coh, S. &Moore, J. E. Designprinciples for shift current photovoltaics. Nat. Commun. 8,14176 (2017).4. Zhang, Y. et al. Switchable out-of-plane shift current in ferroelectrictwo-dimensional material CuInP2S6. Appl. Phys. Lett. 120,013103 (2022).5. Huang, Y.-S., Chan, Y.-H. &Guo, G.-Y. Large shift currents via in-gapand charge-neutral excitons in a monolayer and nanotubes of BN.Phys. Rev. B 108, 75413 (2023).6. Ebrahimian, A., Dadsetani, M. & Asgari, R. Shift current in molecularcrystals possessingcharge-transfer characteristics.Phys. Rev. Appl.19, 44006 (2023).7. Dong, Y. et al. Giant bulk piezophotovoltaic effect in 3R-MoS2. Nat.Nanotechnol. 18, 36–41 (2023).8. Li, Z. et al. An anisotropic van der Waals dielectric for symmetryengineering in functionalized heterointerfaces. Nat. Commun. 14,5568 (2023).9. Yang, S. Y. et al. Above-bandgap voltages from ferroelectric pho-tovoltaic devices. Nat. Nanotechnol. 5, 143–147 (2010).10. Glass, A.M., Linde, D. &Negran, T. J. High-voltage bulk photovoltaiceffect and the photorefractive process in LiNbO3. Appl. Phys. Lett.25, 233–235 (1974).11. Koch, W. T. H., Munser, R., Ruppel, W. & Würfel, P. Anomalousphotovoltage in BaTiO3. Ferroelectrics 13, 305–307 (1976).12. Belinicher, V. I. & Sturman, B. I. The photogalvanic effect in medialacking a center of symmetry. Sov. Phys. Uspekhi 23, 199 (1980).Article https://doi.org/10.1038/s41467-025-58918-9Nature Communications |         (2025) 16:4827 6www.nature.com/naturecommunications13. Sipe, J. E. & Shkrebtii, A. I. Second-order optical response in semi-conductors. Phys. Rev. B 61, 5337–5352 (2000).14. Young, S.M., Zheng, F. & Rappe, A.M. First-principles calculation ofthe bulk photovoltaic effect in bismuth ferrite. Phys. Rev. Lett. 109,236601 (2012).15. Morimoto, T. & Nagaosa, N. Topological nature of nonlinear opticaleffects in solids. Sci. Adv. 2, e1501524 (2016).16. Sun, X. et al. Topological insulator metamaterial with giant circularphotogalvanic effect. Sci. Adv. 7, eabe5748 (2023).17. Zhang, Y. et al. Photogalvanic effect in Weyl semimetals from firstprinciples. Phys. Rev. B 97, 241118 (2018).18. Gao, Y., Zhang, Y. & Xiao, D. Tunable layer circular photogalvaniceffect in twisted bilayers. Phys. Rev. Lett. 124, 77401 (2020).19. Zhang, Y. et al. Switchable magnetic bulk photovoltaic effect in thetwo-dimensional magnet CrI3. Nat. Commun. 10, 3783 (2019).20. Fei, R., Song, W. & Yang, L. Giant photogalvanic effect and second-harmonic generation inmagnetic axion insulators. Phys. Rev. B 102,35440 (2020).21. Watanabe, H. & Yanase, Y. Chiral photocurrent in parity-violatingmagnet and enhanced response in topological antiferromagnet.Phys. Rev. X 11, 11001 (2021).22. Mu, X., Xue, Q., Sun, Y. & Zhou, J. Magnetic proximity enabled bulkphotovoltaic effects in van der Waals heterostructures. Phys. Rev.Res. 5, 1 (2023).23. Wang, H. & Qian, X. Electrically and magnetically switchablenonlinear photocurrent in РТ-symmetric magnetic topologicalquantum materials. NPJ Comput. Mater. 6, 199 (2020).24. Kim, J. S. et al. Electrical transport properties of polymorphicMoS2.ACS Nano 10, 7500–7506 (2016).25. Xie, D. et al. Coplanar multigate MoS2 electric-double-layer tran-sistors for neuromorphic visual recognition. ACS Appl. Mater.Interfaces 10, 25943–25948 (2018).26. Meng, Y. et al. Electrical switching between exciton dissociation toexciton funneling in MoSe2/WS2 heterostructure.Nat. Commun. 11,2640 (2020).27. Kang, J., Li, J., Li, S.-S., Xia, J.-B. & Wang, L.-W. Electronic structuralMoiré pattern effects on MoS2/MoSe2 2D heterostructures. NanoLett. 13, 5485–5490 (2013).28. Zhang, N. et al. Moiré intralayer excitons in a MoSe2/MoS2 hetero-structure. Nano Lett. 18, 7651–7657 (2018).29. Zhang, C. et al. Interlayer couplings, Moiré patterns, and 2D elec-tronic superlattices in MoS2/WSe2 hetero-bilayers. Sci. Adv. 3,e1601459 (2023).30. Lin,M.-L. et al.Moiré phonons in twisted bilayerMoS2.ACSNano 12,8770–8780 (2018).31. Shinokita, K., Watanabe, K., Taniguchi, T. & Matsuda, K. Valleyrelaxation of the moiré excitons in a WSe2/MoSe2 heterobilayer.ACS Nano 16, 16862–16868 (2022).32. Kim, H. et al. Dynamics of Moiré trion and its valley polarization in amicrofabricated WSe2/MoSe2 heterobilayer. ACS Nano 17,13715–13723 (2023).33. Akamatsu, T. et al. A van der Waals interface that creates in-planepolarization and a spontaneous photovoltaic effect. Science 372,68–72 (2021).34. Zhang, S. et al. Observation of the photovoltaic effect in a van derWaals heterostructure. Nanoscale 15, 5948–5953 (2023).35. Hu, C., Naik, M. H., Chan, Y.-H., Ruan, J. & Louie, S. G. Light-inducedshift current vortex crystals inmoiré heterobilayers.Proc. Natl Acad.Sci. USA 120, e2314775120 (2023).36. Strasser, A.,Wang,H. &Qian, X. Nonlinear optical andphotocurrentresponses in Janus MoSSe monolayer and MoS2–MoSSe van derWaals heterostructure. Nano Lett. 22, 4145–4152 (2022).37. Sauer, M. O. et al. Shift current photovoltaic efficiency of 2Dmaterials. NPJ Comput. Mater. 9, 35 (2023).38. Diehl, R. & Carpentier, C.-D. The crystal structure of chromiumthiophosphate, CrPS4. Acta Crystallogr. 33, 1399–1404 (1977).39. Lee, J. et al. Structural and optical properties of single- and few-layer magnetic semiconductor CrPS4. ACS Nano 11,10935–10944 (2017).40. Zhao, W. et al. Metastable MoS2: crystal structure, electronic bandstructure, synthetic approach and intriguing physical properties.Chem. Eur. J. 24, 15942–15954 (2018).41. Kim, S., Lee, J., Lee, C. & Ryu, S. Polarized Raman spectra andcomplex raman tensors of antiferromagnetic semiconductorCrPS4.J. Phys. Chem. C 125, 2691–2698 (2021).42. Houmes, M. J. A. et al. Highly anisotropic mechanical response ofthe Van der Waals magnet CrPS4. Adv. Funct. Mater. 34, 2310206(2023).43. Yang, J. et al. Edge orientations of mechanically exfoliated aniso-tropic two-dimensional materials. J. Mech. Phys. Solids 112,157–168 (2018).44. Tiwari, R. P., Birajdar, B. & Ghosh, R. K. First-principles calculation ofshift current bulk photovoltaic effect in two-dimensional α-In2Se3.Phys. Rev. B 101, 235448 (2020).45. Dharmadhikari, V. S. & Grannemann, W. W. Photovoltaic propertiesof ferroelectric BaTiO3 thin films rf sputter deposited on silicon. J.Appl. Phys. 53, 8988–8992 (1982).46. Kaner, N. T. et al. Enhanced shift currents in monolayer 2D GeS andSnS by strain-induced band gap engineering. ACS Omega 5,17207–17214 (2020).47. Pal, S. et al. Bulk photovoltaic effect in BaTiO3-based ferroelectricoxides: an experimental and theoretical study. J. Appl. Phys. 129,084106 (2021).48. Chang, Y. R. et al. Shift-current photovoltaics based on a non-centrosymmetric phase in in-plane ferroelectric SnS. Adv. Mater.35, 2301172 (2023).49. Liu, W. et al. Graphene charge-injection photodetectors. Nat.Electron. 5, 281–288 (2022).50. Sturman, B. I. & Fridkin, V.M. in The Photovoltaic and PhotorefractiveEffects in Non-Centrosymmetric Materials (Ferroelectricity andRelated Phenomena), Vol. 8 (ed Taylor, G. W.) (Gordon and BreachScience, London, 1992).51. Dai, Z. & Rappe, A. M. First-principles calculation of ballistic currentfrom electron-hole interaction. Phys. Rev. B 104, 235203(2021).52. Sturman, B. I. Ballistic and shift currents in the bulk photovoltaiceffect theory. Phys.-Uspekhi 63, 407 (2020).53. Belinicher, V. I., Ivchenko, E. L. & Sturman, B. I. Kinetic theory of thedisplacement photovoltaic effect in piezoelectrics. Sov. Phys. JETP56, 2 (1982).54. Burger, A. M. et al. Direct observation of shift and ballistic photo-voltaic currents. Sci. Adv. 5, eaau5588 (2024).55. Cui, X. et al.Multi-terminal transportmeasurements ofMoS2 using avan der Waals heterostructure device platform. Nat. Nanotechnol.10, 534–540 (2015).56. Pei, Q. L. et al. Spin dynamics, electronic and thermal transportproperties of two-dimensional CrPS4 single crystal. J. Appl Phys.119, 4 (2016).57. Chen, Q., Ding, Q., Wang, Y., Xu, Y. & Wang, J. Electronic andmagnetic properties of a two-dimensional transition metal phos-phorous chalcogenide TMPS4. J. Phys. Chem. C 124, 12075–12080(2020).58. Peng, Y. et al. Controlling spin orientation and metamagnetictransitions in anisotropic van der Waals antiferromagnet CrPS4 byhydrostatic pressure. Adv. Funct. Mater. 32, 2106592 (2022).59. Son, J. et al. Air-stable and layer-dependent ferromagnetism inatomically thin van der Waals CrPS4. ACS Nano 15, 16904–16912(2021).Article https://doi.org/10.1038/s41467-025-58918-9Nature Communications |         (2025) 16:4827 7www.nature.com/naturecommunications60. Peng, Y. et al. Magnetic structure and metamagnetic transitions inthe van der Waals antiferromagnet CrPS4. Adv. Mater. 32,2001200 (2020).61. Nakamura, M. et al. Impact of electrodes on the extraction of shiftcurrent from a ferroelectric semiconductor SbSI. Appl. Phys. Lett.113, 232901 (2018).62. Hatada, H. et al. Defect tolerant zero-bias topological photocurrentin a ferroelectric semiconductor. Proc. Natl. Acad. Sci. USA 117,20411–20415 (2020).63. Qian, Z., Zhou, J., Wang, H. & Liu, S. Shift current response in ele-mental two-dimensional ferroelectrics. NPJ Comput. Mater. 9,67 (2023).64. Schankler, A. M., Gao, L. & Rappe, A. M. Large bulk piezo-photovoltaic effect of monolayer 2H-MoS2. J. Phys. Chem. Lett. 12,1244–1249 (2021).65. Tinoco, M., Maduro, L. & Conesa-Boj, S. Metallic edge states in zig-zag vertically-oriented MoS2 nanowalls. Sci. Rep. 9, 15602 (2019).66. Mennel, L., Paur, M. & Mueller, T. Second harmonic generation instrained transitionmetal dichalcogenidemonolayers:MoS2,MoSe2,WS2, and WSe2. APL Photonics 4, 034404 (2018).67. Hou, D. et al. Extraordinary magnetic second harmonic generationin monolayer CrPS4. Adv. Opt. Mater. 12, 2400943 (2024).AcknowledgementsThis work was supported by JSPS KAKENHI (Grant Nos. JP16H00910,JP16H06331, JP17H06786, JP19K14633, JP19K22142, JP20H05664,JP21H05232, JP21H05235, JP21H01012, JP21H05233, JP22K18986 andJP23KJ1381), JST FOREST program (Grant No. JPMJFR213K), JST CRESTprogram (Grant No. JPMJCR24A5), the Collaboration Program of theLaboratory for Complex Energy Processes, Institute of AdvancedEnergy, KyotoUniversity.Growthofh-BNwas supported fromGrantNos.JPMXP0112101001, JSPS KAKENHI and JP20H00354.Author contributionsS.A. contributed to the fabrication of samples studied in this work. S.A.,K.S., and K.M. designed the experiments, which were performed by S.A.K.W. and T.T. provided h-BN crystal which used in samples. Data analysiswas performed by S.A. and K.M. The draft was written by S.A., K.S., andK.M., with all authors contributing to reviewing and editing. The projectwas supervised by K.M.Competing interestsThe authors declare no competing interests.Additional informationSupplementary information The online version containssupplementary material available athttps://doi.org/10.1038/s41467-025-58918-9.Correspondence and requests for materials should be addressed toKazunari Matsuda.Peer review information Nature Communications thanks the anon-ymous reviewer(s) for their contribution to thepeer reviewof thiswork. 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If material is notincluded in the article’s Creative Commons licence and your intendeduse is not permitted by statutory regulation or exceeds the permitteduse, you will need to obtain permission directly from the copyrightholder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.© The Author(s) 2025Article https://doi.org/10.1038/s41467-025-58918-9Nature Communications |         (2025) 16:4827 8https://doi.org/10.1038/s41467-025-58918-9http://www.nature.com/reprintshttp://creativecommons.org/licenses/by/4.0/http://creativecommons.org/licenses/by/4.0/www.nature.com/naturecommunications Nonlinear photovoltaic effects in monolayer semiconductor and layered magnetic material hetero-interface with P- and T-�symmetry broken system Results Discussion Methods Sample preparation Photocurrent measurement Magnetic photocurrent measurements Data availability References Acknowledgements Author contributions Competing interests Additional information