Tunable Photodetectors via in situ Thermal Conversion of TiS$_3$ to TiO$_2$

In two-dimensional materials research, oxidation is usually considered as a common source for the degradation of electronic and optoelectronic devices or even device failure. However, in some cases a controlled oxidation can open the possibility to widely tune the band structure of 2D materials. In particular, we demonstrate the controlled oxidation of titanium trisulfide (TiS$_3$), a layered semiconductor that has attracted much attention recently thanks to its quasi-1D electronic and optoelectronic properties and its direct bandgap of 1.1 eV. Heating TiS$_3$ in air above 300 {\deg}C gradually converts it into TiO$_2$, a semiconductor with a wide bandgap of 3.2 eV with ap-plications in photo-electrochemistry and catalysis. In this work, we investigate the controlled thermal oxidation of individual TiS$_3$ nanoribbons and its influence on the optoelectronic properties of TiS$_3$-based photodetectors. We observe a step-wise change in the cut-off wavelength from its pristine value ~1000 nm to 450 nm after subjecting the TiS$_3$ devices to subsequent thermal treatment cycles. Ab-initio and many-body calculations confirm an increase in the bandgap of titanium oxysulfide (TiO$_{2-x}$S$_x$) when increasing the amount of oxygen and reducing the amount of sulfur.


Introduction
Low-dimensional semiconductors are attracting increasing interest in the scientific community working on optoelectronic devices thanks to their outstanding optical and electronic properties combined with reduced dimensionality [1][2][3]. The large surface-to-volume ratio of two-dimensional (2D) materials benefits many applications such as gas-sensing, but it may enhance the sensitivity of these materials to oxidation compared to bulk materials. Moreover, lattice vacancies and atomic-level defect combined with the presence of light can accelerate the oxidation process [4][5][6][7][8], which is typically accompanied by a degradation of the electrical and optical properties reducing the device performance [9][10]. Furthermore, shining high intensity light on 2D materials can induce additional processes of photo-oxidation [11][12][13][14]. The overall performance reduction induced by oxidation seems to be one of the main issues to solve in developing industrial applications based on 2D materials, therefore controlling the oxidation process is a very active subject for both fundamental and applied research in the context of band engineering.
Titanium trisulfide (TiS3) is a layered semiconductor which has attracted much attention recently thanks to its quasi-1D electronic and optoelectronic properties [15][16][17][18] and its direct bandgap of 1.1 eV [19][20][21][22][23][24][25]. Using first-principles calculations, Iyikanat et al. showed that TiS3 can react with various forms of oxygen [26]. An experimental demonstration was given by Molina-Mendoza et al., who reported thermogravimetric analysis (TGA) of bulk TiS3 in oxygen atmosphere showing the partial conversion of the material into TiO2, a large bandgap (3.2 eV) insulator with a wide range of applications [19,[27][28][29]. In this article we investigate the controlled thermal oxidation of individual TiS3 nanoribbons and its influence on the optoelectronic properties of TiS3-based photodetectors. We first study the oxidation of TiS3 powder and single nanoribbons deposited on a glass substrate. Using Raman spectroscopy and optical analysis we can monitor the material properties as a function of time while heating at 320 °C in air. We find that an individual TiS3 nanoribbon converts to crystalline TiO2 in approximately 10 minutes. Control experiments performed on TiS3 nanoribbons fully encapsulated between hexagonal boron nitride flakes confirm that the direct contact between TiS3 and air is necessary for the oxidation process to happen. After establishing the change in material properties we demonstrate the controlled oxidation of a TiS3 nanoribbon photodetector that allows tuning the cutoff wavelength and sensitivity of the device. By monitoring the change in its current-voltage characteristics and in its spectral photoresponse, we find that the cut-off wavelength is blue-shifted upon oxidation, reaching a cut-off wavelength of 450 nm (while it is ≈1100 nm for pristine TiS3 according to previous works [19]). Various intermediate states are observed, demonstrating the tunability of the nanoribbon bandgap. Ab-initio and many-body calculations confirm an increase in the bandgap near to that of titanium oxysulfide (TiO2-xSx) when increasing the amount of oxygen and reducing the amount of sulfur.

Materials Synthesis
The starting TiS3 material was synthetized by a solid-gas reaction using Ti powder and sulfur powder sealed into a quartz ampoule and kept at 550 °C for 20 h. Additional details about the synthesis and elemental characterization of TiS3 can be found in the references [17,30,31]. Figure 1a shows an optical picture of TiS3 powder while Figure 1b shows the same powder after heating it for 5 min at 350 °C in air. After heating the material, we observed a dramatic change of its appearance, with a clear color from black to white, due to the conversion of TiS3 to TiO2. Thanks to the layered structure of TiS3, individual nanoribbons can be isolated by mechanical exfoliation. To study an individual TiS3 nanoribbon, we first exfoliated the powder onto Nitto tape and then transfered part of the flakes from the tape to a viscoelastic polidimethylsiloxane (PDMS) stamp. After the identification, we transfered the chosen nanoribbon to a different substrate (such as glass, SiO2/Si…) with an all-dry deterministic transfer method [32,33]. This is the authors' version (post peer-review) of the manuscript: F Ghasemi et al. Nanomaterials, 10(4), 711, 2020. https://doi.org/10.3390/nano10040711 That has been published in its final form: https://www.mdpi.com/2079-4991/10/4/711 A typical TiS3 nanoribbon transferred onto a glass slide is shown in Figure 1c. The microscope picture is recorded in transmission mode and the nanoribbon appears black since it is absorbing most of the white light due to the bandgap of 1.1 eV. The nanoribbon has a length of approximately 150 µm (oriented along the crystal b axis) and a width of 5 µm (a axis). Figure 1d shows the same nanoribbon after heating it for 5 min at 350 °C in air. The morphology of the nanoribbon appears intact, but the substantial change in color indicates that its absorption, which is related to the bandgap and the band-structure, has changed dramatically. The change from black to white/transparent due to a reduction of the light absorption indicates an opening of the bandgap. A higher resolution picture of the initial and final status of TiS3 nanoribbons can be obtained using electron microscopy. Figure 1ef shows a field emission gun scanning electron microscopy (FEGSEM) image of TiS3 nanoribbons before and after the heat treatment. As can be seen from the images, the nanoribbons morphology is maintained after the heat treatment, although the final nanoribbons show higher roughness.

Thermal Oxidation Analysis
To gain deeper insight into the thermal oxidation process of TiS3 we used TGA coupled to mass spectrometry (MS). Figure 2a shows a TGA curve of TiS3 kept under a flux of 90 mL/min of air and heated at a rate of 10 °C/min. The graph of temperature as a function of time, shown in the top panel of Figure 2a, displays a discontinuity at approximately 30 min, indicative of an exothermic reaction occurring at 300 ± 10 °C. This reaction is accompanied by a loss of approximately 43% of the initial mass (see the bottom panel of Figure 2a) that is consistent with the difference between the mass of This is the authors' version (post peer-review) of the manuscript: F Ghasemi et al. Nanomaterials, 10(4), 711, 2020. https://doi.org/10.3390/nano10040711 That has been published in its final form: https://www.mdpi.com/2079-4991/10/4/711 TiS3 and TiO2 (44%). These results indicate that the conversion of TiS3 into TiO2 takes place under atmospheric conditions starting at 300 °C. A more in-depth look can be achieved using a mass spectrometer to detect the species present during the reaction. Figure 2b shows the ionic currents at m/q = 16, 32 and 48 (m/q is the ration between the atomic mass m and the atomic charge q of the species) as a function of time recorded during the TGA experiment, corresponding to O2 (whose cracking pattern shows two signals) and SO2. The dip observed at 30 minutes in the traces of m/q = 16 and 32 indicated that the O2 present in the atmosphere was reacting with TiS3. At the same time, the peak in current of m/q = 48 is consistent with the liberation of sulfur atoms from TiS3 and their successive reaction with oxygen to form gaseous SO2. The composition of the final product after the thermal treatment of TiS3 was studied with x-ray diffraction measurements (XRD). The x-ray diffraction measurements were performed using a X-pert PRO diffractometer under a θ/2 θ configuration. Figure 2c shows XRD patterns of TiS3 before and after the heating treatment with the main diffraction planes indicated. In the pristine material a single polycrystalline phase is observed, TiS3. All the diffraction peaks in the XRD pattern can be indexed to the phase monoclinic TiS3 in good agreement with the standard JCPDS card no. 00-036-1337. The most intense diffraction peaks at Bragg angles 10.2°, 20.4°, 30.8° and 41.4°are assigned to the (001), (002), (003), (012) and (004) planes. After the heating, the XRD pattern changed significantly. The new diffraction peaks can be indexed to polycrystalline tetragonal TiO2, anatase, whose more intense peaks at angles 25.3°, 38.6°, 37.8°and 48.1° can be attributed to the (101), (004), (112) and (200) planes in good agreement with the standard JCPDS card no. 00-021-1272. Comparing the two spectra it can be seen that the diffraction peaks after the treatment are broader than the ones before, indicating that the produced TiO2 has crystallites of a smaller size. Overall, the previous results support a scenario in which TiS3 heated above 300 °C in ambient conditions undergoes the global exothermic reaction: TiS3 + 4O2 → TiO2 + 3SO2, which converts the trisulfide in anatase TiO2. After characterizing the thermal oxidation of bulk TiS3, we focused on individual nanoribbon oxidation which was interesting for the fabrication of high-quality optoelectronic devices. We started by using Raman spectroscopy to study the composition of a single nanoribbon. Figure 3a shows the This is the authors' version (post peer-review) of the manuscript: F Ghasemi et al. Nanomaterials, 10(4), 711, 2020. https://doi.org/10.3390/nano10040711 That has been published in its final form: https://www.mdpi.com/2079-4991/10/4/711 Raman spectra of a TiS3 nanoribbon recorded in its pristine form (after deposition onto a SiO2/Si substrate) and during a heating cycle with spectra taken every 2 minutes while heating the sample at a temperature of 320 °C. The Raman spectra were recorded in a Raman Microscope (SENTERRA II, Bruker) while illuminating the sample with a laser of 532 nm focused in a circular spot (area ∼2 µm 2 , power 2 mW, power density 1 mW/µm 2 ) and an integration time of 20 s. The power density that we use is lower than the threshold density for photooxidation of the TiS3, which we estimate to be 5 mW/µm 2 (see Section S4 of the Supporting Information). The Raman signal of the pristine TiS3 shows four prominent peaks due to TiS3 and a very weak peak at 520 cm −1 due to the silicon substrate. The peaks at energies 177 cm −1 , 302 cm −1 , 371 cm −1 , and 559 cm −1 correspond to Ag Raman modes of the TiS3 nanoribbon and are in good agreement with the modes reported for bulk TiS3 [34]. After heating up the sample we observe a reduction in the intensity of the TiS3 peaks and an increase in the Si peak intensity during the first two cycles (4 min) that can be attributed to an increase in the transparency of the nanoribbon. After approximately 6 minutes of heating (after three cycles) we observed the quenching of the TiS3 peaks with only the 520 cm −1 Si peak visible in the Raman spectrum of the sample. The spectra recorded after 8, 10 and 12 minutes of heating show the appearance of a new peak centered at 142 cm −1 . This peak is consistent with the signature of an Eg Raman mode of TiO2 [35,36]. The evolution of the Raman spectra of the nanoribbon shows that a pristine TiS3 nanoribbon can be converted to TiO2 by heating at 320 °C. The TiS3 to TiO2 oxidation process can be readily visualized from the plot in Figure 3b in which we show the extracted intensities of the 142 cm −1 (TiO2) and 302 cm −1 (TiS3) peaks as a function of the number of heating cycle. Apart from the change in the Raman signal, we also observe a clear change in the color of the nanoribbon deposited on the SiO2/Si surface from green to yellow during the conversion process as shown in the inset of Figure 3b.
This is the authors' version (post peer-review) of the manuscript: F Ghasemi et al. Nanomaterials, 10(4), 711, 2020. https://doi.org/10.3390/nano10040711 That has been published in its final form: https://www.mdpi.com/2079-4991/10/4/711 To study the role of the environment in the oxidation process of a single nanoribbon we fabricated a hexagonal boron nitride (h-BN) encapsulated TiS3 nanoribbon on top of a transparent indium tin oxide (ITO) substrate. The top panel of Figure 3c shows the schematic of the samples. We first transferred a flake of h-BN onto the ITO surface and then transferred two TiS3 nanoribbons onto the h-BN surface. We finally transferred a second h-BN flake covering just one of the two TiS3 nanoribbons. Figure 3c shows an optical picture of the fabricated stack after heating it. We recorded the Raman spectrum of each nanoribbon before and after heating up the sample at 450 °C (a temperature much larger than the threshold for oxidation of 300 °C). Figure 3d shows the Raman spectra of the two nanoribbons before heating that display very similar features and are both characterized by the four TiS3 peaks discussed above. Notice that compared to Figure 3a the Si peak is missing since the substrate is ITO. When comparing the spectra after heating at 450 °C for 30 min we observe a large This is the authors' version (post peer-review) of the manuscript: F Ghasemi et al. Nanomaterials, 10(4), 711, 2020. https://doi.org/10.3390/nano10040711 That has been published in its final form: https://www.mdpi.com/2079-4991/10/4/711 difference between the two nanoribbons. While the fully encapsulated nanoribbon (2) does not show a significant change in its spectrum, indicating that the final material is TiS3, the unencapsulated flake (1) shows a dramatic change in its spectrum, due to the conversion from TiS3 to TiO2. The encapsulation (with bottom and top h-BN) prevents the oxidation of the TiS3 nanoribbons from happening. The effect of the h-BN layers are visible also in the optical picture of Figure 3c where a big difference in the aspect of the two nanoribbons (one being oxidized and the other not) can be seen. As a side note, the Raman spectrum of the oxidized uncovered nanoribbon shows additional peaks compared to Figure 3a, located at energies of 396 cm −1 , 518 cm −1 and 635 cm −1 . These peaks, associated to the TiO2 crystalline phase, are due to anatase TiO2 in agreement with the results from the XRD measurements of Figure 2c.

Bandgap Energy Calculation
The experiments discussed above show that a thermal oxidation process can convert TiS3 nanoribbons into TiO2 and that this evolution can be followed on a single ribbon level with Raman spectroscopy. We now focus on the changes in the band-structure of the system when passing from TiS3 to TiO2.
To calculate the electronic band structure, we have performed state-of-the-art ab-initio Density Functional Theory (DFT) calculations with a pseudo-potential plane-wave method as implemented in the PWSCF code of the Quantum-ESPRESSO suite [37][38][39]. Figure 4 shows some examples of the electronic band structure calculated with DFT for the TiO2 in the rutile, anatase, IV and V allotropes (see a 3D representation of the different structures in Figure 5a) over the first Brillouin zone. A GW calculation most of the time opens up the band gap with a rigid shift of the conduction bands.  Figure 5a correspond to the ones of the lowest total energy, which are most likely to be formed during the oxidation process. Similar techniques have been applied to find the structures for the fully oxidized states. For these structures, we have also performed a GW calculation to evaluate the band gap. Both DFT and GW show an increase in the gap at the -point of the band structures of interest for these experiments, ranging from about 1eV for TiS3 to about 3 eV for the TiO2 in the rutile structure. For intermediate oxidation states, the evaluation of the actual atomic configuration is more difficult since one should consider exceedingly large super cells to build the possible atomic configurations, but our results show clearly an increase in the DFT band gap from 0.31 eV for TiS3 to about 0.7 eV for the partially oxides structures, to more than 2 eV for the TiO2 in the different allotropic forms. These results are consistent with others already present in the literature for TiO2. Figure 5a shows the calculated bandgap of TiS3 (left), intermediate Ti2S3O2 phases (middle) and of four different polytypes of TiO2 (right). The different materials are ordered along the horizontal axis according to the total energy (when going from left to right the total energy decreases and the thermodynamic stability increases). Because DFT typically underestimates the band gap energy [40], we have further performed a more refined calculation for some of the structures based on non-selfconsistent GW method. The left panel of Figure 5b shows a FEGSEM image of such a nanoribbon in which the core and the edges show a different contrast. The Energy-dispersive X-ray spectroscopy (EDX) analysis of the image performed in the center and at the edges of the nanoribbon reveals a higher oxygen concentration along the edges. This indicates that the oxidation process occurs through the formation of intermediate phases TiO2-xSx at the ribbon surface that form a sheath around TiS3. This phenomenon is also visible in the microscope pictures of partially oxidized nanoribbons in Figure S2, Section S1 of the Supporting Information.

Electronic and Optoelectronic Characterization
After the change in the optical appearance and vibrational properties of TiS3 nanoribbons after high temperature treatment due to the oxidation of TiS3 to TiO2 was established, we then investigated electronic transport through an individual nanoribbon and monitored the change of the optoelectronic properties. We fabricated a TiS3 photodetector by transferring an individual TiS3 nanoribbon onto two pre-patterned platinum electrodes separated by a distance of 20 µm. The electrical measurements were carried out in atmospheric conditions using a home-built probestation equipped with a source measure unit (Keithley 2450). For the optoelectronic measurements the devices were illuminated by focusing the light of different high-power fiber-coupled LED sources with different emission wavelengths (Thorlabs), forming a circular spot (400 µm in diameter) onto the surface of the sample. The total optical power reaching the sample was measured with a silicon photodetector (Thorlabs power meter PM100D with sensor S120VC). Figure 6a shows a schematic of the device and an optical image of the pristine TiS3 device. The TiS3 nanoribbon bridges the two electrodes and light can be shined on the exposed TiS3 channel to study its photoresponse. Figure 6b shows the current-voltage characteristics (I-Vs) of the device recorded just after the fabrication (top panel) and after heating it for 12 min at 320 °C (bottom panel). From previous measurements the electrical resistivity of the exfoliated TiS3 thin nanoribbons is ~0.1 Ω·cm [15] while measurements on macroscopic TiS3 whiskers, reported by Gorlova et al., reach 2 Ω·cm [41]. Photographs of the device at various stages of the evolution are shown in Figure S6, Section S3 of the Supporting Information. The I-Vs were recorded in dark conditions (black curve) and under global illumination at 405 nm with power density 1 W/cm 2 (purple curve). Comparing the I-Vs of the pristine with those of the oxidized device we can see a difference in the shape of both I-Vs and in the magnitude of the current. The TiS3 device is characterized by linear I-Vs and current in the range of µA while the oxidized device has non-linear I-Vs with currents in the pA (approximately six orders of magnitude lower than the pristine device). In both cases the device responds to light, evidenced by the larger current observed in the I-Vs under illumination at 405 nm in comparison to the ones recorded in the dark. Considering that the area of the channel is 100 µm 2 and that the incident optical power is 1 W/cm 2 , the responsivity of the device to 405 nm at 3 V (−3 V) is 8 A/W (11 A/W) in the pristine (TiS3) case and 0. 16 mA/W (0. 22 mA/W) in the oxidized case. In total in this work we fabricated and characterized 11 devices that have been heated at 320 °C in air, see Section S3 of the Supporting Information. In four cases out of 11 we observed the conversion of the TiS3 photodetector in a TiO2 one without losing the functionality (success rate 36%).
In order to study the responsivity of the device to different wavelengths and incident optical powers we measure current-time traces (at fixed bias voltage) while switching ON and OFF in time with the incident light. Figure 6c shows various photocurrents versus time traces measured with wavelengths in the range between 375 nm and 660 nm. At the beginning of the measurement the light is switched OFF and the current passing through the device has only the dark current contribution. When switching ON the illumination (approximately at time = 5 s in the plot), the current passing through the device rapidly increases thanks to the additional contribution given by the photogenerated current. By extracting the current difference between the OFF and ON illumination, we can calculate the photocurrent and responsivity of our device. From the plot in Figure 6c one can see that This is the authors' version (post peer-review) of the manuscript: F Ghasemi et al. Nanomaterials, 10(4), 711, 2020. https://doi.org/10.3390/nano10040711 That has been published in its final form: https://www.mdpi.com/2079-4991/10/4/711 the responsivity of the TiS3 pristine device decreases when increasing the wavelength of the incident radiation. Figure 6d shows the photocurrent of the pristine device at 405 nm for different values of the illumination power density showing larger values for higher incident powers. Figure 6e-f shows similar measurements to those shown in Figure 6c-d made on the oxidized nanoribbon photodetector. These measurements show that after oxidation the photocurrent decreases and the time response increases. Moreover, the photodetector responds only to light with a wavelength shorter than 405 nm. The cut-off wavelength of the photodetector (defined as the largest wavelength for which the photodetector shows a response higher than the noise level 2 × 10 −6 A/W), is larger than 660 nm in the pristine case and blue-shifts to 405 nm in the oxidized state. As a control experiment we heated one device in high vacuum conditions (pressure ∼10 −5 mbar) to test the effect of heat in the absence of oxygen, see Section S2 of the Supporting Information. This device maintained the photodetecting properties of TiS3 (responsivity spectrum and cut-off wavelength) even after 30 min at 320 °C. That has been published in its final form: https://www.mdpi.com/2079-4991/10/4/711 while modulating the intensity of the incident light with a square wave on the pristine TiS3 photodetector (c-d) and on the TiO2 (e-f). The colors in (c,e) correspond to different incident wavelengths (375 nm, 405 nm, 420 nm, 530 nm, 605 nm, 660 nm) while the shades of purple in (d,f) correspond to different incident power densities from 0.02 W/cm 2 to 1 W/cm 2 at a fixed wavelength of 405 nm.
From current-time traces similar to the ones in Figure 6c-f we extracted the responsivity of the device, in its pristine state and after subsequent heating cycles, as a function of wavelength and incident power. Figure 7a shows the evolution of the wavelength-resolved responsivity of the device measured at an incident power of 100 nW during the heating process. The pristine device has a responsivity of approximately 1 A/W that after the first heating cycle decreases to 10 −4 A/W. The dependence on the wavelength also gets modified by the heating process. While in the first three traces the device responds to all the probed wavelengths from 375 nm to 660 nm, in the last four traces the responsivity shows an abrupt decrease for wavelengths larger than 450 nm, indicating that there is a blue-shift of the cut-off wavelength of the photodetector. The wavelength-resolved responsivity reported in the initial and final stages of the device are compatible with previously reported spectra of TiS3 and TiO2 photodetectors [17,42].  That has been published in its final form: https://www.mdpi.com/2079-4991/10/4/711 where is a dimensionless exponent, which assumes a value of −0.5 in the case of a photodetector dominated by bimolecular recombination between photoexcited carriers or at high injection levels (band-to-band) and 0 in the case of monomolecular recombination or low injection levels (trap-assisted) [43,44]. The log-log plot shown in Figure 6b reveals that our device is characterized by a negative for all the heating cycles since the slope of each curve in the figure gives directly the exponent . Figure 7c shows the extracted cut-off wavelength and the exponent of the device as a function of the heating cycle. The evolution of the cut-off wavelength (here defined again as the largest wavelength for which the photodetector shows a response higher than the noise level 2 × 10 −6 A/W) is consistent with the predicted bandgap evolution shown in Figure 4a. As can be seen the exponent starts from a value of −0.42 which indicates that the pristine TiS3 device is mostly dominated by bandto-band recombination (0 heating cycle). After the first heating cycle the exponent decrease to a value of −0.7 that is the minimum value observed for . In the subsequent heating cycles (2-6) we observe a gradual increase in the value of the exponent toward 0, signifying an increase in the density of traps and/or an effect on the lower effective light injection levels due to the lower absorption in the visible range of the spectrum by the TiO2 (see Section S1 of the Supporting Information). The exponent saturates around −0.25, a value larger than the starting value of −0.4, which indicates that the final TiO2 material contains a larger trap density than the starting TiS3 material that favors monomolecular recombination between photoexcited carriers [45,46].

Conclusions
In conclusion, we studied the thermal oxidation of TiS3 nanoribbons with optical spectroscopy showing that this material can be gradually converted to anatase TiO2 in a controlled way. We built photodetectors based on single TiS3 nanoribbons and we tuned their cut-off wavelength by gradually oxidizing the nanoribbons. We observe that the oxidation also induces a decrease in the responsivity, which could have practical implications for the applicability of the TiO2-xSx, as a larger detector area would be required to obtain the same photocurrent. Ab-initio calculations of the band-structure of the materials are in agreement with the experiments. The shift of the cut-off wavelength in our photodetectors with a simple annealing step, demonstrates the ability to tune on-demand the bandgap of the TiO2-xSx for novel applications.

Section S2 -TiS3 photodetector annealed in vacuum
As a control experiment, to investigate the influence of the temperature in absence of oxygen, we studied a TiS3 photodetector that we heated above 320 °C in vacuum. Figure  S4a shows the responsivity of the device in its pristine state (red curve) and after 10, 20 and 30 minutes at 320 °C in vacuum. The shape of the responsivity (and the power exponent in panel b) is preserved and the device shows an almost flat response from less than 400 nm to more than 700 nm (as can be also seen in panel c), typical of TiS3 photodetectors. Figure S4: a) Responsivity of the device as a function of wavelength. The pristine TiS3 device (top) was heated at 320 °C in vacuum in steps of 10 minutes and after each step This is the authors' version (post peer-review) of the manuscript: F Ghasemi et al. Nanomaterials, 10(4), 711, 2020. https://doi.org/10.3390/nano10040711 That has been published in its final form: https://www.mdpi.com/2079-4991/10/4/711 the responsivity was measured. Note that the dark current decreases for the successive heating cycles from 70 µA (pristine) to 20, 1.1 and 0.025 µA for the 1 st , 2 nd and 3 rd heating cycle respectively. b) Responsivity exponent as a function of heating cycle. c) Cut-off wavelength as a function of heating cycle.

Section S3 -TiS3 photodetectors annealed in air
In our study we characterized a total of 12 TiS3 photodetecting devices, 11 devices have been heated above 320 °C in air (devices 1-11) and 1 device has been heated above 320 °C in vacuum as a control experiment. When heating up the device in air we managed to successfully convert the TiS3 photodetector in a TiO2 photodetector without losing the functionality in 4 devices, corresponding to a success rate of 36%. Figure S5a shows the responsivity as a function of wavelength of devices 1-11 each in its pristine state and Figure S5b shows the responsivity of devices 1-4, which have been successfully converted to TiO2 photodetectors, in their initial and final states.    Figure S7: a) Optical microscope image of a TiS3 photodetector (device 2) just after fabrication (left panel) and at different steps of the heating process. b) Responsivity of the device as a function of wavelength for different heating cycles. The pristine TiS3 device (top) was heated at 320 °C in steps of 2 minutes and after each step the responsivity at different wavelengths was extracted. The two bottom curves correspond to the oxidized TiO2 device. c) Responsivity of the device at 405 nm as a function of incident power for the pristine device (top curve) and after consecutive heating cycles. c) Responsivity-power law exponent as a function of heating cycle.

Section S4 -Stability of TiS3 during Raman spectroscopy
We performed measurements of TiS3 ribbons at various incident optical power densities and integration times to probe the stability of TiS3 during the Raman spectroscopy experiments. The results, which are collected in Figs. S8 and S9, indicate that TiS3 ribbons undergo photooxidation at an incident power of 10 mW (spot size ∼2 um 2 , power density 5 mW/µm 2 ). In the case of lower densities we do not observe any degradation or photooxidation for exposition times as large as 60 s. This is the authors' version (post peer-review) of the manuscript: F Ghasemi et al. Nanomaterials, 10(4), 711, 2020. https://doi.org/10.3390/nano10040711 That has been published in its final form: https://www.mdpi.com/2079-4991/10/4/711 Figure S8a shows a semilogarithmic representation of the Raman spectra of a TiS3 ribbon recorded for different incident powers (in sequence 0.2 mW, 2 mW, 5 mW, 10 mW, 20 mW, 0.2 mW) and different integration times. In all the three panels one can see that the spectra recorded at the lowest excitation power of 0.2 mW in the pristine state and after the application of the larger powers are different. While the pristine spectrum (red) shows only the peaks due to TiS3, the final spectrum shows an additional peak at 142 cm -1 , due to TiO2, independent on the integration time. This indicates that the laser at 532 nm used in the Raman experiments can oxidize the TiS3 ribbons. Figure S8b shows the spectra recorded with integration time 10 s with a vertical offset added for clarity. From these spectra it is clear that the additional peak at 142 cm -1 appears during the measurement at 10 mW. To quantify this phenomenon we perform a fit of the peaks at 142 cm -1 (due to TiO2) and at 301 cm -1 (due to TiS3) indicated by the shaded areas in panel b. Figure S8c shows the ratio between the areas of the peaks at 301 cm -1 and 142 cm -1 as a function of the incident power. By inspecting the plot we see that the ratio between the peaks is constant for powers as large as 5 mW (power density 2.5 mW/µm 2 ) and that rapidly decreases to zero (in an irreversible way) at a power of 10 mW (power density 5 mW/µm 2 ). In the case of an incident power equal or lower than 5 mW we do not observe any laser induced oxidation for integration times as long as 60 s as can be seen in Figure S9.
This is the authors' version (post peer-review) of the manuscript: F Ghasemi et al. Nanomaterials, 10(4), 711, 2020. https://doi.org/10.3390/nano10040711 That has been published in its final form: https://www.mdpi.com/2079-4991/10/4/711 Figure S8: a) Raman spectroscopy of a TiS3 ribbon as a function of illumination power (curves with different colours) and integration time. For each integration time (4 s, 10 s and 20 s) we select a different position in the ribbon to probe the pristine material. b) Raman spectra recorded with integration time 10 s at different incident powers. Each spectrum is normalized by the incident power. A vertical offset has been introduced for clarity. c) Ratio between the areas of the peaks at 301 cm -1 (related to TiS3) and at 142 cm -1 (TiO2) as a function of power.