1. Ablation thresholds, rates, and efficiencies
Determining ablation thresholds, rates, and efficiency is essential for optimizing femtosecond laser material processing and ensuring consistent results. The ablation threshold is the minimum laser fluence required to start the ablation process, and it is one of the most important parameters in laser material processing. The ablation rate (i.e., the amount of material removed per unit of time) is dependent on the laser fluence and pulse duration, while the efficiency of ablation considers the ablation rate and the laser power used. We ablated a series of grooves, varying the laser fluence between the groove for each of the three laser wavelengths. We used a saw-tooth line drive waveform scanning approach in the single-shot-per-spot regime to ensure that no thermal accumulation may result from pulse overlaps. The results are presented in Table 1 and Fig. 1.
UV irradiation had the lowest ablation threshold, at 0.6 ± 0.1 J/cm2 for enamel and 0.10 ± 0.05 J/cm2 for dentin, followed by green with 0.85 ± 0.05 J/cm2 (enamel) and 0.10 ± 0.05 J/cm2 (dentin), and then IR irradiation at 1.0 ± 0.1 J/cm2 (enamel) and 0.5 ± 0.1 J/cm2 (dentin). The optimal regime for ablation of enamel in a single pulse per shot regime was similar for both IR and green irradiation, with 0.9 ± 0.1 mm3/min/W in the range of (4.5–8.5) J/cm2 for IR and (7.0–9.0) J/cm2 for green.
The ablation efficiency of dentin was almost two times higher for IR with 1.74 ± 0.05 mm3/min/W, and almost 4.5 times higher for green irradiation with 4.00 ± 0.05 mm3/min/W. Green irradiation was the most effective for the ablation of both enamel and dentin, with an ablation rate ~ 2.3 times higher than IR for dentin.
UV caused visually discernible modification of the grooves for all tested fluences, thus the optimal ablation efficiencies are not presented in Table 1. Figure 1 presents the evolution of the depth per pulse and the ablation efficiencies as a function of the laser fluence. While the highest ablation rate can be achieved using green irradiation, this requires dynamic control over the fluence when crossing the enamel and dentin boundary to maintain the highest efficiency.
Analysis by optical microscopy and by scanning electron microscopy of the ablated grooves in enamel and dentine revealed no damage to the tooth structure around the grooves and on the groove floors, and very precise cuts in the enamel and dentin, as seen in Fig. 2a., for both IR and green wavelengths. The grooves were investigated by scanning electron microscopy and confirmed crack-free preparations in teeth, as also observed in previous studies [17–19]. However, grooves with UV irradiation had carbonization and charring on the walls and floors, as shown in Fig. 2b.
2. Effect of pulse overlap
The overlap of laser pulses can have a marked effect on the results of ablation. The overlap refers to the interval between two consecutive laser pulses during the scanning, and it can affect efficiency, quality, and precision. If the overlap between laser pulses is too large, the material may be subject to excessive heating, which can result in damage to the material or changes in its physical properties. This occurs because the energy from one pulse is absorbed by the material and this causes a temperature rise that is not completely dissipated before the next pulse arrives, leading to cumulative heat effects. Precise control of laser pulse overlap is essential to achieve the desired results. This can be done by adjusting the repetition rate of the laser pulses or the scanning speed of the laser beam.
Grooves in enamel and dentin were prepared by varying the overlap between the laser pulses. Overlaps of 25, 50, 75, and 90% of the spot diameter were tested. For both IR and green, in enamel and dentin, no damage was observed by optical microscopy for up to 50% of pulse overlap. Charring started to occur with 75% overlap from 2.5 J/cm2, as seen in Fig. 2b. At 90% overlap, damage was observed for all fluences for both enamel and dentin. For the UV wavelength, all processed grooves showed charring of the walls and floors of the grooves, Fig. 3.
3. Investigation of structural modifications by Raman spectroscopy
Raman spectroscopy was performed on the walls and floors of the laser-processed grooves [20–23]. Figure 4 presents the Raman spectra taken on unprocessed enamel (Fig. 4a) and enamel irradiated at different wavelengths (Fig. 4b and 4c). Attributions of the peaks were done elsewhere [3]. Briefly, the symmetric stretching of phosphate units (PO4) in apatite is visible at 959 cm− 1. Additional vibrations of PO4 can be observed at 427 cm− 1 and 584 cm− 1 (bending) and at 1041 cm− 1 (antisymmetric stretching). The peak at 1070 cm− 1 was attributed to the symmetric stretching of carbonate units (CO3), overlapping with the stretching of PO4. After irradiation with the IR and green wavelengths, no structural change was observed in enamel for all tested fluences and for pulse overlaps from a single shot regime to 50% overlaps. No structural change was observed for UV irradiation in the single pulse regime and for 50% overlap up to 12.7 J/cm2. Above this value, all peaks disappeared from the spectra, as illustrated in Fig. 4c. At 75% pulse overlap and fluences above 10 J/cm2, charring was observed with a complete loss of features on the Raman spectra. This indicates severe damage to the enamel, and those fluences and high pulse overlaps should be avoided to preserve the structural integrity of the material.
Figure 5 presents the Raman spectra taken on unprocessed dentin (Fig. 5a) and dentin irradiated at different wavelengths (Fig. 5b to 5d). Dentin exhibits additional organic peaks at 1240 cm− 1, attributed to a mix of C-N stretching and N-H bending vibrations in amide III, at 1455 cm− 1 attributed to the wagging of CH2, and at 1665 cm− 1 attributed to the in-plane stretching of carbonyl in peptide bonds [3]. The other bands are artifacts from the low signal-to-noise ratio and baseline correction. For clarity, grey bands indicate where the peaks are located. After irradiation with the IR wavelength (Fig. 5b), no changes were observed on the spectra with no pulse overlap at all tested fluences, or at 50% pulse overlap. Structural modifications of the dentin were visible for all laser fluences at 75% overlap (visible charring). No characteristic peaks were observed on the spectrum at this overlap. For green irradiation, disappearances or broadening of peaks in the dentin spectra are observed at laser fluences above 2.0 J/cm2 for 50% overlap. In particular, the organic peaks in the 1200–1700 cm− 1 range disappear, and the intensity of the main PO4 feature at 959 cm− 1 decreases significantly. Hence, to avoid damage, pulse overlaps of 50% and above should be avoided. The dentin can be safely laser processed for all tested laser fluence with no pulse overlap at all (i.e., a single pulse regime) and up to 50% overlap for IR irradiation and for green irradiation below 2.0 J/cm2.
For UV irradiation (Fig. 5d), structural changes occurred even at the low fluence of 0.6 J/cm2 in the single pulse regime (with no pulse overlap). A decrease in the signal-to-noise ratio was observed, and the peaks were poorly resolved. The disappearance of organic peaks above 1200 cm− 1 and PO4 bending at 427 cm− 1 was noted. At 50% of pulse overlap, damage occurred in dentin from 0.6 J/cm2 as illustrated by the disappearance of the organic peaks above 1200 cm− 1, the bending of PO4/carbonate peaks, and stretching (below 600 cm− 1 and around 1000 cm− 1). At a laser fluence of 14.0 J/cm2 and above, the phosphate and organic peaks completely disappeared, and broad bands appeared in the 1200–1600 cm− 1 range indicating carbonization. For 75% of pulse overlap, severe damage was noted, resulting in complete loss of the Raman features in the spectra. Overall, with the UV wavelength, the poor resolution of the Raman spectra and loss of the Raman signatures of both enamel and dentin indicates that UV irradiation is highly damaging to healthy tooth structures, even at laser fluences below the ablation threshold of dentin, and thus UV should be avoided for the laser processing of teeth.
Overall, Raman spectroscopic studies revealed that IR and green were the most suitable wavelengths for tooth ablation. IR and green could safely process healthy tooth structure, avoiding structural damage in enamel and dentin when the laser pulse overlap was below 50%. However, a laser fluence below 2.0 J/cm2 must be used for green irradiation to prevent any damage to the dentin, which also corresponds to the optimal ablation efficiency for green irradiation. UV irradiation was not suitable for tooth ablation in all the tested conditions.
4. Investigation of temperature changes inside teeth during laser processing
Elevations in temperature inside the pulp chamber (nerve canal) of the tooth during laser processing are presented in Table 2 for all laser wavelengths for two different fluences: 3.0 and 6.0 J/cm2, giving an effective average laser power of 0.5 W and 1 W, respectively. No external cooling was applied to the tooth during the experiment. A temperature increase below the maximum allowable limit of 5.5˚C [24] was seen for both IR and green, for all tested pulse overlaps at a fluence of 3.0 J/cm2. At a fluence of 6.0 J/cm2, the temperature increase after IR irradiation was below the threshold, for 0 and 25% of pulse overlap, but overpassed the threshold by 1.5 degrees for 50% overlap and by 2.5 degrees for 75% overlap. On the contrary, the temperature increase for green irradiation at 6 J/cm2 was above the limit for all tested degrees of overlap. UV irradiation caused a temperature increase above the limit for all tested conditions, especially when at 6.0 J/cm2.
The same experiments were reproduced with a flow of compressed air directed to the ablation region on the tooth. All tested laser fluences and pulse overlaps showed a temperature increase below 0.5°C for both enamel and dentin for all three laser wavelengths.