Laser photonic-reduction stamping for graphene-based micro-supercapacitors ultrafast fabrication

Micro-supercapacitors are promising miniaturized energy storage devices that have attracted considerable research interest. However, their widespread use is limited by inefficient microfabrication technologies and their low energy density. Here, a flexible, designable micro-supercapacitor can be fabricated by a single pulse laser photonic-reduction stamping. A thousand spatially shaped laser pulses can be generated in one second, and over 30,000 micro-supercapacitors are produced within 10 minutes. The micro-supercapacitor and narrow gaps were dozens of microns and 500 nm, respectively. With the unique three-dimensional structure of laser-induced graphene based electrode, a single micro-supercapacitor exhibits an ultra-high energy density (0.23 Wh cm−3), an ultra-small time constant (0.01 ms), outstanding specific capacitance (128 mF cm−2 and 426.7 F cm−3) and a long-term cyclability. The unique technique is desirable for a broad range of applications, which surmounts current limitations of high-throughput fabrication and low energy density of micro-supercapacitors.

In Fig. 4, authors have demonstrated shape versatility of MSC devices. I doubt all the devices that have the same geometrical are or not. Although they have normalized it with the area, however different areas will contribute to different mass loading of the devices. Therefore it is recommended to keep a similar area of the devices and compare the gravimetric capacitance as well during the optimization of shape versatility.
When MSC manufacturing is focusing on the manuscript, one should check the stability of the devices with respect to cycling performances.

REVIEWER NO. 1 1.0 Reviewer's Comments
"This work reported a reduced graphene oxide/MnO 2 micro supercapacitors fabricated by a spatially shaped ultrafast laser. The authors declare that more than 30,000 capacitors can be "stamped" within 10 min and a single capacitor displays the energy density of 0.23 Wh/cm 3 , outstanding specific capacitance of 128 mF cm -2 /426.7 F cm 3 . I found that the manuscript is presented in a very unclear mode with wrong descriptions and lots of parts are misled. These mistakes limit the novelty this work could display. This manuscript should be rejected or at least rewritten/resubmitted for new review by elucidating at least the following issues:

Our Response
Thank you for your detailed and invaluable feedback and for your time and effort in reviewing our manuscript. Your constructive feedback has helped us revise our manuscript, which has enabled us to improve the quality of our manuscript.
Per your comments, we have revised the instances of unclear and incorrect phrasing in our manuscript. Therefore, starting from the title and abstract, we have rearranged the manuscript and extensively modified and rewritten it to highlight the innovative points of our study in our responses from 1.1 to 1.4.

Physics and chemistry of GO reduction and MnO 2 for enhanced capacitance
is well investigated. This work does not present any new knowledge on these fields. Figs 1&2 are not presented in a proper way. Fig. 2 (c-f) are basically conducted by a patterned mirror. The simultaneous reduction from the patterned beam is effective and valued. But the authors failed to explain why they need 10 min. This indeed unveil if the authors properly explain the laser reduction mechanism, either the same as or different from the well understanding results (photothermal, or non-thermal mechanism). Fig. 3s display a lateral resolution is 500 nm, slightly bigger than half of wavelength (800 nm). This indicates a limited thermal reduction by short pulses. Unfortunately, this manuscript does not unveil this physics.

The laser reduction (so-called stamping in this manuscript) through a holographic mirror (SLM) in
It is fine to focus on manufacturing novelty (if there is any in this work). For a holographic mirror, it is critical to explain the mechanism to complete a 3D reduction without z-scan as a conventional 3D stage. In another word, the authors should present the thickness if they electrically create a flat mirror in SLM. Again unfortunately, in fig. 3 (a, b), authors do not display either the thickness resolution or total thickness they create. This is very misled. The thickness resolution can tell how thin they can write with a holographic mirror and the total thickness directly relates to the intrinsic advantage of a holographic mirror. I do not need guess or deduce which values they should be. But without these, it is hard to know if their calculation of energy density/specific capacitance are correct. Even worse, these formulae provided in the main text and the supplementary materials do not automatically explain how a holographic mirror complete a z-scan. Therefore, Fig. 1 are totally misled. The "stamp" in the title is also misled since the physics is still photonic reduction. A minor mistake is that the authors have to document how the gas releases from the reduced body. If they are trapped, a porous structure will be formed and how this porosity affects the energy storage performance.

Our Response
Thank you for your constructive suggestions, which have helped us improve the quality of our manuscript. Because this problem involves several aspects, we shall segregate this question into several parts to supplement our response and appropriate revisions.

"Physics and chemistry of GO reduction and MnO 2 for enhanced
capacitance is well investigated. This work does not present any new knowledge on these fields."

Our Response
First, in this study, we achieved photochemical synthesis of graphene and manganese dioxide by using a spatially shaped femtosecond laser (SSFL) for micro-supercapacitors (MSCs), with a three-dimensional (3D) porous composite structure constructed in only one step. This is indeed a novel method of fabricating laser-induced graphene (LIG)/MnO 2 MSCs. The photoinduced reaction mechanism of graphene oxide (GO) and Mn 2+ is different from the traditional reduction mechanism.
The obtained 3D porous composite material is more conducive to improved capacitance.
(1) Technological superiority in the fabrication of LIG/MnO 2 composite materials Graphene/manganese dioxide composites can improve the capacitive performance of supercapacitors. To ensure the combination of the two materials is highly robust, GO and manganese salt precursors are often used in combination, and redox reactions are used to dope graphene and manganese dioxide. The traditional method involves the use of strong oxidants to promote reactions leading to the synthesis of LIG/manganese dioxide. For example, when using the strong oxidizer potassium permanganate R1.1-3 , the reaction can be described as follows: 4 2 4 2 2 4 2 2 4KMnO +3C+2H SO 4MnO +2K SO +3CO +2H O → (E1-1) The C atoms of LIG can convert Mn 7+ into Mn 4+ , leading to the initial formation of MnO 2 nanostructures on LIG, which, in turn, facilitate further growth R1.4 . GO undergoes thermal reduction, leading to the formation of LIG. However, it is difficult to precisely regulate the reduction process and meet the needs of microdevice fabrication. Additionally, this method of chemical reduction often requires the reaction process to be conducted using an extra current collector and relies on the current collector for supercapacitor assembly. Chen et al R1. 5 reported a composite of GO and MnO 2 fabricated on a nickel foam current collector with high capacitance through the interaction between GO and MnO 2 , which is possible because the oxygen functional groups of GO act as anchor sites for MnO 2 growth. In other studies R1.6,7 , graphene/MnO 2 composites have been fabricated through spinning or rolling, which require the construction of a current collector or stripping of the gap through other processes.
However, to construct better structures and thus enhance the performance of supercapacitors, studies have reported 3D heterogeneous structures. He et al R1.8 reported 3D graphene/MnO 2 MSCs with high areal capacitance. A specially treated Ni foam template can play the role of the skeleton for graphene grown through chemical vapor deposition, aiding construction of a highly porous graphene network for a high loading mass of electrodeposited MnO 2 . Fei et al R1. 9 used a metal foam as a 3D skeleton, performed hydrothermal growth of manganese dioxide nanoparticles on the metal foam, and used plasma-enhanced chemical vapor precipitation to produce graphene quantum dot/MnO 2 heterostructural materials.
By contrast, we used a novel SSFL method to fabricate LIG/MnO 2 MSCs. In this study, MSCs were rapidly fabricated using a SSFL in one step in situ. The mixed sample underwent simultaneous oxidation of Mn 2+ to MnO 2 and reduction of GO to 3D laser induced graphene (LIG). LIG-wrapped MnO 2 was thus successfully synthesized. During this process, oxidants, current collectors, and metal foam for the 3D structure were not required. More importantly, a femtosecond laser was employed to control the chemical reaction process to synthesize composites.
(2) Photochemical regulation of the LIG/MnO 2 synthesis mechanism Femtosecond lasers have ultrahigh peak power (>10 13 W cm −2 ) and ultrashort irradiation periods, and femtosecond laser fabrication has the unique advantage of nonlinear nonequilibrium processing R1. [10][11][12] . When light and matter interact, at such high peak intensity, seed electrons are primarily generated through strong electric field ionization (multiphoton ionization and tunneling ionization) and are unrelated to the initial state of the material. Ultrafast localized nonlinear absorption leads to spatial confinement of radiation-induced material changes in a focal volume R1. 13 .
Moreover, the ultrashort pulse is shorter than most of the relevant physical and chemical characteristic time scales, resulting in chemical reaction pathways and chemically selective molecular excitation that can be effectively controlled using the femtosecond laser. On adjusting the laser fluence to control photoinduced or photothermally induced reduction and oxidation, the valence state of manganese oxide can be well regulated.
Hence, femtosecond laser fabrication is certain and repeatable. Furthermore, the nonequilibrium effects of the femtosecond laser potentially facilitate photon-electron coupling before the lattice is altered. Electrons are excited from the bonding state to the antibonding state, weakening C-O electron bonding near the top of the valence band, resulting in direct removal of oxygen atoms. However, as the number of femtosecond laser pulses increases, the thermal effect becomes even stronger, resulting in photothermal lysis of the carbon bond structure and an increase in the number of lattice defects R1.14 . The intensity of femtosecond laser pulses provides adequate kinetic energy to oxygen atoms such that they exit the graphene sheet in gaseous form without imparting large kinetic energy to carbon atoms R1. 15 .
We propose an interesting photosynthetic route for synthesizing LIG-MnO 2 in  Femtosecond lasers provide numerous photons that excite electrons to create free-moving electrons and holes. Through their action, GO reduced to LIG and Mn 2+ was absorbed on the negatively charged region of the hydrophilic oxygen functional groups of GO owing to electrostatic effects. Before laser processing, a mixture of GO and manganese acetate solutions was completely degraded ultrasonically.
GO-wrapped Mn 2+ particles were thus obtained. Mn 2+ facilitates GO reduction because of its higher oxidation potential R1. 16,17 , and Mn 2 uses anchor sites in GO for oxidation to MnO 2 nanoparticles in situ R1. 18 . Simultaneously, GO deoxygenation releases energy, which functions as an in situ power source driving the new oxidation reaction of Mn 2+ R1. 19 .
Thermal GO deoxygenation is initiated by a small amount of heat, and as the process continues, both temperature and energy increase, corresponding to the energy released during the reduction of GO and sufficient to propagate and sustain GO reduction R1. 20 . The amount of heat released during the GO deoxygenation reaction is several times that required to drive the endothermic oxidation of metal ions R1. 19,21 .
The equations for the reaction are as follows:       Thus, the femtosecond laser reduces GO, simultaneously facilitating the action of metal ions, which is a novel mechanism of action. Consequently, GO reduction and MnO 2 synthesis are mutually reinforcing processes in shaped femtosecond laser radiation. By altering the pulse energy, materials of various LIG/manganese oxide compositions were successfully synthesized through photomodulation of reaction mechanisms. By using an SSFL, the Mn 4+ percentage could be maximized, and MnO 2 is the primary component of LIG/manganese oxide.
(3) Unique laser-induced graphene/MnO 2 composites for enhanced capacitance The unique femtosecond laser regulated the chemical reaction, enabling synthesis of an excellent composite material with 3D structure. Capacitance is enhanced using an approach that employs materials wherein ions are inserted between atomic layers, resulting in charge storage R1.22 . These materials can be described as a 2D structure designed to achieve rapid ion transfer between atomic layers. Graphene is a crucial 2D material and has attracted increasing attention owing to its theoretically large specific surface area (~2630 m 2 g −1 ) R1.23 , excellent electrical conductivity R1. 24 and mechanical flexibility, and other desirable characteristics.
However, pure graphene sheets continue to demonstrate certain limitations in terms of practical application because of their low capacitance. As an alternative to precious metal oxides, MnO 2 has exceptional performance, including high theoretical capacity, and other advantages, such as low price, abundant reserves, and environmental friendliness. However, the poor electronic conductivity of manganese dioxide results in high internal resistance of the electrode R1. [25][26][27] . To foster strengths and circumvent weaknesses, we designed the LIG/manganese dioxide composite electrode. Moreover, for the 3D patterned structure fabricated through a one-step reaction by using a shaped laser, graphene is used as a solid skeleton, and the uniform effect of the light field facilitates favorable distribution of MnO 2 nanoparticles on the graphene skeleton.
As shown in Figure R1.6, the porous structure provides a rapid path and several path choices for ion transfer, facilitating rapid and complete interaction of ions and thus quicker charging and discharging. The 3D porous scaffold is very stable, potentially mitigating mechanical stress within the electrode and enabling long-term cycling stability of electrochemical energy storage systems R1. [28][29][30] . Our 3D LIG network is supported by MnO 2 nanoparticles, such that the composite provides adequate space for electrolyte ions to interact with the entire electroactive surface of the electrode, facilitating efficient charge storage. Graphene not only supports MnO 2 nanoparticles but also has a strong connection with each MnO 2 nanoparticle, preventing the aggregation of MnO 2 nanoparticles and resolving the graphene layer restacking issue, thus enhancing electron transport and stability during cycling R1. 19 . The two types of composite material are conducive to high capacitance.

Modifications
According to the comments of the reviewer, we have revised the corresponding part in our manuscript.
The original part form Page 3, Paragraph 2, Line 7 to Line 20 is as flowing: "The SFLS strategy can simultaneously realize high-precision and ultra-efficient processing of large-scale multiple L-S-MSCs. Benefiting from the straightforward technology, the efficiency of processing L-S-MSCs has been unprecedentedly improved, and thousands of flexible L-S-MSCs could be precisely fabricated in 1 minute. Due to the special uniform light field effect brought by the spatially shaped femtosecond (ss-fs) laser, we have created the structure different from Gaussian light processing which is conducive to the formation of three-dimensional structures and avoid the incomplete processing caused by the uneven light intensity regionalization.
Therefore, we transiently synthesize LIG with the uniformly distributed MnO 2 nanoparticles in situ, and simultaneously pattern the novel fluffy and porous three-dimensional composite structures with ultrahigh specific surface area and toughness. Mn 2+ can facilitate the reduction process of graphene oxide (GO) due to the higher oxidation potential 22,23 and use the anchor sites provided by GO to be oxidized to MnO 2 nanoparticle in situ 24 . In this way, the fabricated LIG/MnO 2 L-S-MSCs are collector-free, arbitrary graphics, ultra-flexible, high-resolution, tens of micrometers in size with high specific capacitance and ultrahigh energy density." These parts are revised as following: "The SSFL strategy can perform high-precision and ultraefficient processing of large-scale multiple MSCs in one step. Femtosecond lasers are uniquely characterized by their ultrahigh peak power (>10 13 w cm -2 ) and ultrashort irradiation period 22,23 . The composites of LIG/MnO 2 are synthesized through photomodulation of the reaction mechanisms (photochemical and photothermal reduction/oxidation) 24 . Mn 2+ can facilitate the graphene oxide (GO) reduction process of because of its high oxidation potential 25,26 , and it ca use the anchor sites provided by GO to be oxidized to MnO 2 nanoparticle in situ 27 . At the same time, a fluffy porous three-dimensional structure with ultrahigh specific surface area and toughness can be obtained. The process does not require oxidants, current collectors, demanding reaction conditions, addition of chemicals or metal foam. Furthermore, this SSFL technique is particularly attractive because it is suitable for numerous material systems benefiting from the universality of materials for femtosecond laser processing. The SSFL strategy has ultrahigh efficiency and consistently fabricates high-performance, high-resolution, and flexible MSCs, which is promising for application to advanced miniaturized electronics, such as microelectromechanical systems. This strategy also provides a pathway for high throughput in the industry and designable large-scale flexible energy storage devices." The original part in Page 10, Figure 3  The original part form Page 11, Paragraph 1, Line 1 to Line 10 is as flowing: " Fig. 3 proposed an enlightening photosynthetic route for synthesizing LIG/MnO 2 at the atomic level. From the schematic diagram, we can clearly observe that in the area irradiated by ss-fs laser, the carbon-oxygen bond is significantly reduced, and a large amount of MnO 2 is generated. In the areas without laser irradiation, more carbon-oxygen bonds and Mn 2+ exist on GO film. Therefore, the role of ss-fs lasers in synthesizing materials and building three-dimensional structures is very obvious. The ss-fs laser provides a large amount of photon energy, which promotes the autocatalysis of GO, which in turn produces electrons for the reduction of GO. Mn 2+ will be absorbed on the negatively charged part of the hydrophilic oxygen functional groups of GO. During the reduction of graphene oxide, Mn 2+ undergo oxidation to become MnO 2 using the energy and oxygen functional groups provided by the GO deoxidation process." These parts are revised as following: As the reaction continues, the photothermal reduction gradually emerges, and the cumulative effect of the pulsed laser produces heat, which results in the pyrolysis of GO, whereby oxygen-containing functional groups such as hydroxyl (-OH), carboxyl (-COOH), and oxygen Bridges (C-O-C) are break up into CO, CO 2  Therefore, the SSFL reduction in the experiment was caused by the combined effect of photochemical and photothermal reactions. Our findings indicated that gas was released when the SSFL reduced GO composite film, which is crucial in the formation of 3D porous structure composites. The 3D porous patterned structure fabricated in one step using the SSFL employed graphene as a solid skeleton, and the uniform effect of the light field enabled manganese dioxide nanoparticles to be evenly distributed on the graphene skeleton. The pores functioned as shortcuts for rapid ion diffusion between graphene layers, which increased the speed of ion transport across the compressed film. The 3D porous scaffold was very stable, which would mitigate mechanical stress within the electrode and thus ensure the stability of long-term cycling of electrochemical energy storage systems 41,42 . Therefore, the LIG/MnO 2 composite had improved capacitance." The original part in Page 9, Paragraph 1: "Analytical characterization of the LIG/MnO 2 . Fig. 3a and b depict the cross-sectional view of the hybrid film before and after the ss-fs laser patterning. The original graphene oxide layers were stacked tightly together. Interestingly, after ss-fs laser ablation, the lamellar graphene fluffed up and many MnO 2 nanoparticles were attached to LIG. The SEM revealed the surface of the graphene film also became porous and fluffier after ss-fs laser ablation ( Fig. 3c and d). The fluffy and wrinkled structure resulted in larger specific surface area, fast ion transport, and excellent electrochemical performance." These parts are revised as following: "Mechanism and analytical characterization of LIG/MnO 2 3D composite synthesis using the SSFL. The mechanisms of laser reduction presented in this study fall into two main categories: photochemical and photothermal reduction/oxidation. In the initial stage of SSFL interaction with materials, the photochemical reduction/oxidation induces nonthermal ultrafast electron excitation, nonlinear absorption, and subsequent oxygen group removal because of the ultrashort pulse width and ultrahigh intensity of the SSFL. The instantaneous intensity of the SSFL provides sufficient kinetic energy to enable oxygen atoms to leave the graphene sheet without damaging it 37 ." The added part is inserted following Page 9, Paragraph 1, Line 1 is as following: "During the SSFL reduction process, the effect of photothermal reduction/oxidation became increasingly apparent as the laser fluence was increased.
By altering the laser fluence, LIG/Manganese oxides were successfully synthesized through photomodulation of the reaction mechanisms (photochemical and photothermal reduction/oxidation). We varied the laser fluence (170-290 mJ cm -2 ) of the SSFL to investigate differences in conductivity and electrochemical characterization and identify the optimal reduction/oxidation effect. The resistance and conductivity of the material reached their minimum and maximum, respectively, when the laser fluence was 210 mJ cm -2 (Supplementary Fig. 7 and 8), which implies that the LIG/Manganese oxides composite has large potential capacitance 43 . As expected, the measured area-specific capacitance of the LIG/MnO 2 MSC was highest under the laser fluence of 210 mJ cm -2 ( Supplementary Fig. 9). We investigated whether the high-performance electrode materials were successfully synthesized under the interaction of photochemical and photothermal reduction/oxidation at this laser fluence.
The X-ray diffraction (XRD) patterns of the as-prepared GO and LIG/MnO 2 nanocomposite synthesized under the laser fluence of 210 mJ cm -2 were analysed (Fig.   3b). The most intensive peak of GO at 2θ = 11.2°corresponds to the (001) reflection.  Fig. 10). The different XRD patterns exhibited similar peaks, which could be all well indexed to plane of the α-MnO 2 structure. However, when the laser fluence was considerably lower or higher than 210 mJ cm -2 , one or two other weak peaks appeared, and the peak intensities in the XRD patterns were lower.
The Raman spectra were extremely similar when the laser fluence was between 170 and 290 mJ cm -2 ( Supplementary Fig. 11). We compared the Raman spectra in three cases-untreated, fs-laser modified, and fs-laser reduced-on the basis of the laser fluence (Fig. 3c). Clear G bands were characteristics of sp 2 hybridized C-C bonds at The added part is inserted following Page 9, Paragraph 2, Line 6 is as following: "X-ray photoelectron spectroscopy (XPS) was used to assess the difference before ( Supplementary Fig.12) versus after SSFL ablation under a laser fluence of 210 mJ cm -2 ( Fig. 3d-f). The C 1s spectrum consisted of three peaks: C-C/C=C (284.8 eV), (photothermal, or non-thermal mechanism)."

Our Response
Thank you for your careful review of our manuscript and your suggestions for the improvement of its quality.
In this work, we mentioned that the processing time of 10 minutes is only to form a specific concept of our technology to compare with other work. This study demonstrated that a processing duration of only 10 min could be achieved using the proposed technology ("More than 30,000 laser-stamped MSCs can be produced in 1 cm 2 within 10 min"), which, when compared with the fabrication speed when other methods are used, reflects the ultrahigh speed of the proposed processing technology.
We use the Ti:sapphire laser regenerative amplifier system, which can generate 1,000   Figure 1 b displays that the spatially shaped 3D light field can quickly realize the processing of patterned MSCs. This process realizes the one-step plasticity and reduction of the MSC, which is very close to the form of the stamping, so we call it the laser stamping. Figure 1 c illustrates that the 3D patterned light field is irradiated on the surface of GO hybrid film, thus realizing the three-dimensional reduction and structure of laser-induced graphene/MnO 2 .
Considering the opinions of the reviewer, we have defined the previous statements more specifically to eliminate misunderstandings. We used the laser photonic-reduction stamping to more vividly represent our processing technology.
This laser photonic-reduction stamping process does not require masks and can be arbitrarily changed to achieve ultrafast fabrication of high-solution MSCs with different shapes.
Each individual patterned MSC in Figure 3(c-f) is processed by a single shaped laser. Since a thousand spatially shaped laser pulses can be generated in one second, we can process many MSCs by controlling the movement of the translation stage. As shown in Figure 3e and f, we can easily fabricate tens of thousands of MSCs and make them integrated into a specific pattern by controlling the movement of the translation platform.   We deeply appreciate the detailed and constructive suggestions of the reviewer.
Regarding the mechanism underlying laser reduction, we did not explain this sufficiently clearly in the manuscript. As indicated in our previous response, the femtosecond laser has ultrahigh peak power (>10 13 W cm −2 ) and ultrashort irradiation period, and femtosecond laser fabrication has the unique advantage of nonlinear nonequilibrium processing, providing numerous photons that trigger the generation of electrons and holes.
Numerous thermal treatment approaches including near-field scanning hot tips R1.37,38 and continuous-wave or quasicontinuous pulsed laser irradiation R1. 31 Furthermore, the most efficient shape and intensity of the pulse imparts adequate kinetic energy to oxygen atoms, such that the O atoms exit the graphene sheet without imparting significant kinetic energy to carbon atoms despite the heavier mass of the O atom than the C atom, thus providing conceptual clarity regarding the mechanism underlying the shaped femtosecond laser reduction of GO. This process is suitable for femtosecond lasers with a small pulse width and does not damage the graphene C-C structure or cause local thermal effects.
Upon laser irradiation on the plane of the GO/Mn 2+ film, the electrons in the valence band absorb the photon energy of the laser and jump to the conduction band.
Under the effect of these mobile electrons and holes, GO hybrid films undergo a reduction reaction.
The relevant equation is as follows: This reaction mechanism is schematically illustrated in Figure R1. 9 The high power of the shaped femtosecond laser used herein means that GO is adequately irradiated locally on several occasions. This process results in the photothermal reduction of GO and a porous graphene structure. Because two-photon or multiphoton absorption may occur under the effect of certain compact focusing ultrafast lasers and laser-induced thermal relaxation is common, the femtosecond laser reduction achieved in this study results from the combinatorial effect of photochemical and photothermal effects.

Modifications
According to the comments of the reviewer, we have revised the corresponding text in our manuscript to better illustrate the ultrahigh efficiency of our technology without confusion. This part is revised as following: "laser direct writing" The more precise statement added to the original part in Page 2, Paragraph 2, Line 10 is as flowing: "multiple-spot laser direct writing" The added part is inserted in Page 3, Paragraph 2, Line 5, the detail is as following: "The initial Gaussian beam can be made to various beam shapes by using phase modulations, similar to a variable 3D "photonic stamp", which can pattern the MSCs with designable shapes and photoregulate the chemical reactions to synthesize LIG/MnO 2 ." The added part is inserted in Page 9, Paragraph 2, Line 3, the detail is as following: "Each individual patterned MSC in Figure 3 c and f is processed by a single pulse SSFL. We can easily fabricate tens of thousands of MSCs and make them integrated into a specific pattern by controlling the movement of the translation platform." The original part form Page 6, Paragraph 1, Line 1to Line 9 is as flowing: "The ss-fs laser can achieve ultra-fast fabrication of various-shapes L-S-MSCs ( Fig.   1b). Notably, such high fabrication efficiency for flexible L-S-MSCs is rare, and ss-fs laser also demonstrates high machining accuracy and near faultless processing consistency, which enable rapid and large-scale applications. Under present conditions, we could process 3,000 L-S-MSCs in 1 minute. This rate was tens or hundreds of times more efficient than previously reported processes of MSCs [28][29][30][31][32][33] . As the Table   shows We used the Ti: sapphire laser regenerative amplifier system, which can generate 1,000 single pulses per second. In theory, a single MSC could be fabricated in only 1 millisecond. The actual processing speed observed was more than 3,000/min, which is tens or hundreds of times more efficient than previously reported processes for fabricating MSCs [31][32][33][34][35][36] . The SSFL also has the advantages of high machining accuracy and near faultless processing consistency, enabling rapid and large-scale application.
As illustrated in the Table,  writing of the focal spot is realized by controlling the movement of the translation stage. Therefore, in actual processing, we consider the stability of the translation stage and repeated positioning accuracy to ensure the consistency of processing; multipatterned rapid processing is difficult to achieve. The incident beams (Gaussian beams) were transformed into arbitrary geometric target beams in SLM by programming phase patterns; the shaped beams were then transmitted on the hybrid GO films. The shaped femtosecond laser can be formed in one step and alters the shape by changing the phase pattern. The spot of the shaped laser is a designable pattern that can directly and instantaneously complete patterned MSCs. In conjunction with the advantages of laser direct writing, this technology greatly improves processing efficiency and achieves consistency for large-area processing. In theory, this process is instantaneous.
The more explanations of the laser reduction mechanism are added into the new  can be removed 40 . When the GO is cracked, the energy and accumulated heat in the reaction provide the original energy for oxidation to the manganese ions, thus completing the formation of manganese oxide.
Therefore, the SSFL reduction in the experiment was caused by the combined effect of photochemical and photothermal reactions. Our findings indicated that gas was released when the SSFL reduced GO composite film, which is crucial in the formation of 3D porous structure composites. The 3D porous patterned structure fabricated in one step using the SSFL employed graphene as a solid skeleton, and the uniform effect of the light field enabled manganese dioxide nanoparticles to be evenly distributed on the graphene skeleton. The pores functioned as shortcuts for rapid ion diffusion between graphene layers, which increased the speed of ion transport across the compressed film. The 3D porous scaffold was very stable, which would mitigate mechanical stress within the electrode and thus ensure the stability of long-term cycling of electrochemical energy storage systems 41,42 . Therefore, the LIG/MnO2 composite had improved capacitance.
During the SSFL reduction process, the effect of photothermal reduction/oxidation became increasingly apparent as the laser fluence was increased.
By altering the laser fluence, LIG/Manganese oxides were successfully synthesized through photomodulation of the reaction mechanisms (photochemical and photothermal reduction/oxidation). We varied the laser fluence (170-290 mJ cm -2 ) of the SSFL to investigate differences in conductivity and electrochemical characterization and identify the optimal reduction/oxidation effect. The resistance and conductivity of the material reached their minimum and maximum, respectively, when the laser fluence was 210 mJ cm -2 (Supplementary Fig. 7 and 8), which implies that the LIG/Manganese oxides composite has large potential capacitance 43 . As expected, the measured area-specific capacitance of the LIG/MnO2 MSC was highest under the laser fluence of 210 mJ cm -2 ( Supplementary Fig. 9). We investigated whether the high-performance electrode materials were successfully synthesized under the interaction of photochemical and photothermal reduction/oxidation at this laser fluence."  Fig. 1 are totally misled. The "stamp" in the title is also misled since the physics is still photonic reduction."

Our Response
Thank you very much for your detailed comments on this article.
As indicated in the comments, for a femtosecond laser (wavelength, 800 nm), the diffraction limit should be half the wavelength. During laser direct writing, breaching the diffraction limit is difficult using the line width accuracy of ablation. However, the SSFL can be used to breach the diffraction limit.
In general, we can transform Gaussian light into shaped light to form patterned light spots, resulting in the laser extruding a narrow gap, breaching the diffraction limit. As indicated in Figure R1.10, we designed the light field with different narrow gaps to obtain processed MSCs with differing narrow gaps. As indicated in our manuscript, the size and shape of our SSFL can be controlled, including the narrow gap of the interdigital MSCs. During practical processing, the sensitivity of two-dimensional graphene composites to femtosecond lasers is not as high as that of other metallic materials, and their layered structures would be slightly stacked upon laser irradiation. Therefore, we performed spatial light field shaping to transform the original Gaussian light beam into a 3D laser for processing. Our pattern is a complete MSC pattern; hence, patterns with an ultranarrow gap of even a few nanometers can be theoretically designed.
However, during actual processing, we achieved a narrow gap of 500 nm for the convenience of subsequent electrochemical analysis, considering light field interference.
We report a method of one-step processing of MSCs by using a patterned shaped laser. When shaping the light field, the laser is a 3D light field. As shown Figure   R1.12, different 3D light fields were designed using algorithms.
In order to demonstrate the ability of high-resolution fabrication of our technology, we patterned a simple shape of MSCs to demonstrate a higher resolution of electrode gaps ( Figure R1.11-1). We can see that we patterned parallel strip-shaped MSCs with different narrow gaps so that the gap is a straight line and can be shown more clearly. In the figure, we can see that the resolution of the slit is less than 500 nm, and even close to 350 nm in some parts. Our resolution is realized through the pattern design of light field shaping. In this way, the slit between design patterns is used to achieve the highest resolution, which is not limited by the laser wavelength. It maybe can explain the way to complete a 3D reduction by the 3D shaped laser. In order to demonstrate the machining resolution of our technology, we carried out higher-resolution experiments using the SSFL. We designed the MSC with the shape of two rings, and the distribution of the light field is shown in figure R1.11-2 (a). The high-resolution patterning is realized by adjusting the narrow gap between the two rings, the figure R1.11-2 (b) shows the SEM images of the patterns with different narrow gaps. We can clearly see that the narrow gap can be designed with the shaped laser, and we got the ultra-small narrow gap of 11.6 nm, which is well beyond the traditional diffraction limit. The results of nanometer precision benefit from the design of shaping light fields. We report a method of one-step processing of MSCs by using a patterned shaped laser. When shaping the light field, the laser is a 3D light field. As shown Figure   R1.12, different 3D light fields were designed using algorithms. We regulated the size, narrow gap, and depth of the 3D light field by using an algorithm and software. We designed a 3D light field of 15 × 15 μm 2 to 100 × 100 μm 2 with a depth of 15 μm. As observed in Figure R1.12, the light fields had a regular shape and could be extended along the z-axis. Because the SSFL has a uniform light field on each plane along the z-axis, excellent 3D reduction could be achieved when processing the GO hybrid film.
During actual processing, the thickness and actual processing depth of the GO film, determined using the shaping laser, should be considered. As shown in Figure   R1.13, the shaping laser can simultaneously reduce graphene and synthesize manganese oxide particles in a layered material. Owing to the extremely high peak energy of the femtosecond laser, the GO film can be reduced along three dimensions. During reduction, MnO 2 nanoparticles are generated and become attached to the graphene layered structure, increasing the spacing in the graphene layer and yielding a 3D composite material. Furthermore, gases are released during the reduction, which is one of the reasons for the 3D porous structure of graphene. To determine the actual processing depth, we analyzed scanning electron microscopy (SEM) images of the GO hybrid film before and after shaped laser processing ( Figure R1.14). The cross-sectional images verified our previous conclusion that upon laser irradiation, the layer spacing of GO hybrid films was increased and MnO 2 nanoparticles became adhered.    respectively, all within 2.3 to 2.5 μm, thus reflecting that upon SSFL irradiation of the surface of the GO hybrid film, the spacing of the GO film layer is increased and laser-induced graphene/MnO 2 was synthesized. On the surface, differences in the z-axis between the laser-reduced heterostructure and region without laser processing are obvious. Combined with the aforementioned cross-sectional SEM images, we thus proved the processing capacity of the SSFL along the z-axis, and a porous 3D composite material was synthesized using an SSFL.
For a microscale energy storage device, complete harnessing of the limited potential to boost areal capacitance and energy density is critical. In brief, the 3D expandability of MSCs based on the planar configuration is of great significance. The increase in thickness improves the areal capacitance and energy density, concurrent with our aforementioned objectives. Additionally, we must consider the volumetric capacitance and energy density. To elucidate the 3D machining potential of our technology, we used SSFL irradiation only on one surface of the 5-µm-thick hybrid film. Because the film is very flexible, it can be easily stripped away. After processing using the shaped femtosecond laser, characterization tests were performed using Raman spectroscopy, XPS, and XRD on both surfaces of the irradiated film. On comparing the ablative conditions of both surfaces of the film processed using a laser, it could be determined whether our SSFL completed 3D processing, especially along the z-axis.
In the Raman spectrum of both surfaces of the irradiated film ( Figure R1.18  Using different characterization methods, we concluded that when the shaped femtosecond laser irradiated GO film with a certain thickness from the anterior surface, the processing effect was consistent on both sides of the irradiated composite film, indicating that our 3D femtosecond laser can process materials along the z-axis to complete 3D processing, and the material on the underside of the film still has a favorable reduction effect. With an increase in the scan rate, the difference in the areal capacitance caused by thickness gradually decreased.  Thank you for your meticulous efforts and kind assistance in reviewing our manuscript. As previously stated, our study used designable 3D spatial light to achieve processing along the z-axis. To reinforce the concept of simple, one-step molding, we used a "stamp," which is similar to a postmark, to describe this technology. Compared with the traditional stamp, our optical "stamp" can be arbitrarily changed. Considering the opinions of the reviewer, we have defined the previous statements more specifically to eliminate misunderstandings. We used the laser photonic-reduction stamping to more vividly represent our processing technology. This laser photonic-reduction stamping process does not require masks and can be arbitrarily changed to achieve ultrafast fabrication of high-solution MSCs with different shapes. And our laser photonic-reduction is different from the traditional stamping, which is not a mechanical process but a one-step photonic-reduction process. In order to more vividly reflect the ultrfast, one-step shaping characteristics of our technology, we define the laser photonic-reduction stamping.

Modifications
According to the comments of the reviewer, we have added the corresponding part in our manuscript to better illustrate the high-resolution strategy for fabricating MSCs.
The original part form Page 7, Paragraph 1, Line 13 to Line 18 is as flowing: "L-S-MSCs of various shapes are in the tens to hundreds of micrometers in length. In such a machining precision, our technology has obtained a satisfactory machining effect. Supplementary Fig. 2 clearly displays the regular electrode morphology. The spacing could be adjusted by designing different light field, and the narrow gap of the L-S-MSCs is only 500 nm ( Supplementary Fig. 3). The varying sizes can be controlled by designable light fields from 15×15 μm 2 to 100×100 μm 2 ( Supplementary Fig. 4)." This part is revised as following: "The shape of the spot could be designed, and the size of the spot could be regulated by transforming the target light field. The size of the spot determined the size of the entire MSC, because the MSCs of various shapes were patterned using the SSFL in one step. The varying sizes can be controlled by designable laser spots from 15×15 μm 2 to 100×100 μm 2 ( Supplementary Fig. 3). We could transform Gaussian light into shaped light to form the patterned light spots and use the SSFL to extrude the narrow gap of patterns that could break the diffraction limit. MSCs with different narrow gaps could be fabricated by designing different light fields, and a MSC with a narrow gap of 500 nm was fabricated using SSFL on a GO hybrid film ( Supplementary Fig. 4)." According to the comments of the reviewer, we have added the corresponding part in our manuscript to explain the 3D reduction of the SSFL.
The added part is inserted in Page 5, Paragraph 1, Line 3, the detail is as following: "We used the optimized algorithm to regulate the optical field region, in which the beam width and z-axis propagation distance represented the basic parameters of a 3D optical field. We arbitrarily altered the parameter design to control the size of the optical field and the fixed depth for 3D processing within a certain range. An excellent 3D reduction was achieved in the processing of GO hybrid film because the SSFL had a uniform light field on each plane in the z-axis direction." The original part form Page 9, Paragraph 1, Line 1 to Line 4 is as flowing: " Fig. 3a and b depict the cross-sectional view of the hybrid film before and after the ss-fs laser patterning. The original graphene oxide layers were stacked tightly together. Interestingly, after ss-fs laser ablation, the lamellar graphene fluffed up and many MnO 2 nanoparticles were attached to LIG." This part is revised as following: "The 3D porous structure irradiated by SSFL could be clearly observed on the cross-sectional view and the surface of the hybrid film before and after the SSFL patterning (Fig. 2d). The original GO layers were stacked tightly. Notably, after SSFL To demonstrate the high-resolution fabrication of our technology, we patterned a simply shaped MSC to demonstrate the higher resolution of the electrode gaps. We patterned parallel strip-shaped MSCs with different narrow gaps so that the gap is a straight line and is clearer to see. As shown, the resolution of the slit is less than 500 nm, and close to 350 nm in some parts. Our resolution was realized through the pattern design of light field shaping, where the slit between design patterns was used to achieve the highest resolution but was not limited by the laser wavelength. This potentially explains how to complete a 3D reduction using the 3D shaped laser." The original title is as following: "Ultrafast laser-stamping for MSCs manufacturing" The title is revised as following: "Laser photonic-reduction stamping for graphene-based MSCs ultrafast fabrication" The added part is inserted in Page 3, Paragraph 2, Line 5, the detail is as following: "The initial Gaussian beam can be made to various beam shapes by using phase modulations, similar to a variable 3D "photonic stamp", which can pattern the MSCs with designable shapes and photoregulate the chemical reactions to synthesize LIG/MnO 2 ."

"A minor mistake is that the authors have to document how the gas
releases from the reduced body. If they are trapped, a porous structure will be formed and how this porosity affects the energy storage performance."

Our Response
As indicated in our previous response regarding the mechanism underlying graphene reduction, the shaped femtosecond laser induces photochemical reduction and photothermal reduction during graphene reduction R1. 49  The equation can be expressed as follows A few free electrons are present in the air and absorbed by air's constituent gases.
Of the gases comprising air, oxygen has the highest capacity for adsorbing free electrons. In the presence of these free electrons, GO films are also reduced. The primary equation can be expressed as follows: When laser power causes photothermal reduction, the temperature of the femtosecond laser is relatively low, and the cycloaddition reaction of oxygen bridges (C-O-O) close to each other primarily occurs on the surface of the GO film, and O 2 is generated after GO reduction R1.51 .
If the power density of the laser continues to increase and the surface temperature of the GO film is high, the GO film undergoes a drastic cracking reaction at high temperature, wherein oxygen-containing functional groups including hydroxyls (-OH), carboxyls (-COOH), and oxygen bridges (C-O-C) are decomposed into CO, CO 2 , and H 2 O, being eliminated. Upon elimination of the oxygen-containing functional groups, GO is reduced.
When the SSFL reduces the GO hybrid film, gas is released, which is a critical factor underlying the formation of 3D composite porous structures.
We explain the effect of the characteristics of the porous structure on energy storage performance from several perspectives as follows.
Owing to their high surface area, remarkable thermal conductivity, and excellent electronic conductivity and mechanical properties, porous materials have received increasing attention and their capacitance has been increased compared with solvated electrode materials, particularly at high current density. Porous structures are favorable for fast ion and electron transport and facilitate sufficient contact between electrolytes and porous materials R1.52 .
Pores facilitate rapid ion diffusion between graphene layers and increase the speed of ion transport across a compressed film. As indicated in Figure R1.23, the porous structure provides a rapid and numerous pathways for ion transfer, enabling rapid and complete interactions between ions and the electrode material, meaning that charging and discharging can occur more rapidly. This ability to optimize charge transport was reflected through Nyquist and Bode plots R1.53 . In our study, the MSC displayed an ultraquick response (0.01 ms) and low equivalent series resistance (0.85 mΩ cm −2 ).  As indicated in Figure R1.24, under the same scanning rate, the CV curves of the two supercapacitors almost coincided, indicating that the supercapacitor generated using the SSFL had highly stable capacitance characteristics. Figure  After 6,000 cycles, the GCD curve was still almost identical to the initial curve.
When the voltage window was small, the capacitance retention was almost 100%, and when the voltage window was 2 V, the capacitance retention rate remained >93%, indicating that the MSCs had excellent cycling stability.
The obtained 3D porous scaffold is highly stable and can mitigate mechanical stress within the electrode, ensuring the long-term cycling stability of electrochemical energy storage systems R1.54,55 . Our 3D structure is supported by the MnO 2 nanoparticles, which serve as nanospacers for the LIG network and provide adequate space for electrolyte ions to interact with the entire electroactive surface of the electrode, facilitating efficient charge storage. Not only does graphene serve as a support for the MnO 2 nanoparticles, it also interacts robustly with the MnO 2 nanoparticles, preventing their aggregation and resolving the graphene layer restacking issue, which enhances electron transport and stability during cycling R1.56 .

Modifications
According to the comments of the reviewer, we have revised the corresponding part in our manuscript.
The original part form Page 9, Paragraph 1, Line 3 to Line 6 is as flowing: "The SEM revealed the surface of the graphene film also became porous and fluffier after ss-fs laser ablation ( Fig. 3c and d). The fluffy and wrinkled structure resulted in larger specific surface area, fast ion transport, and excellent electrochemical performance." This part is revised as following: "The 3D porous structure irradiated by SSFL could be clearly observed on the cross-sectional view and the surface of the hybrid film before and after the SSFL patterning ( The porous structure provided a faster path and more path choices for the ion transfer. This enabled the ions to contact the electrode material quickly and fully, thus charging and discharging more quickly. This ability to optimize charge transport is shown in Nyquist plots and Bode plots. Our MSCs exhibited an ultra-small time response (0.01 ms) and low equivalent series resistance (0.85 mΩ/cm 2 )." The added part is inserted in Page 11, Paragraph 1, Line 1, the detail is as following: "Therefore, the SSFL reduction in the experiment was caused by the combined effect of photochemical and photothermal reactions. Our findings indicated that gas was released when the SSFL reduced GO composite film, which is crucial in the formation of 3D porous structure composites. The 3D porous patterned structure fabricated in one step using the SSFL employed graphene as a solid skeleton, and the uniform effect of the light field enabled manganese dioxide nanoparticles to be evenly distributed on the graphene skeleton. The pores functioned as shortcuts for rapid ion diffusion between graphene layers, which increased the speed of ion transport across the compressed film. The 3D porous scaffold was very stable, which would mitigate mechanical stress within the electrode and thus ensure the stability of long-term cycling of electrochemical energy storage systems 41,42 . Therefore, the LIG/MnO2 composite had improved capacitance." The added part is inserted in Page 19, Paragraph 3, Line, 1 the detail is as following: "Furthermore, our MSCs exhibited excellent performance in power density, reaching 136 W cm −3 . The electrochemical tests were carried on the MSC fabricated over 30 days and the capacitance performance is almost the same as the newly prepared MSC, which demonstrates the super stability of our MSCs ( Supplementary   Fig, 27). Furthermore, we obtained the CV curves of the same single." The corresponding content added in Supporting Information is as following: To verify the stability of our MSC, we conducted electrochemical tests on the miniature supercapacitor fabricated after 30 days. We found that it exhibited almost the same electrochemical performance as the initial MSC. As shown, under the same scanning rate the CV curves of the two supercapacitors almost coincided. This also indicated that the supercapacitor prepared using a shaped femtosecond laser has highly stable capacitance characteristics." Fig. 4 (a) displays that their capacitor is pretty worse even at 1V/s, a pretty low scanning rate. The unit of Fig. 4

(h) is ohm/cm2. Without the thickness a unit in ohm
is better to display the internal resistance."

Our Response
We deeply appreciate the careful efforts and kind help of the reviewer in commenting on our paper. These detailed comments will be extremely valuable in making improvements.
We found that the parallel strip MSC exhibits poor performance at 1 V/s in the experiment. Our detailed explanation for this phenomenon is as follows.
Our technology can fabricate the one-step processing of MSCs of any shape. To further highlight the shape diversity and performance uniformity of our MSCs, we constructed several shape-designable MSCs; namely concentric circle, parallel strip, and interdigital. We then recorded the true CV curves of these MSCs at the different scan rates shown in Figure 4.
Regrettably, we placed the worst-performing parallel strip MSC at the beginning of Figure 4, which may have led the reviewer to misunderstand the performance. In   The equivalent series resistance, which is a measure of the total resistance of a system, is determined from the Nyquist plots. As mentioned in our previous response, the thickness of the MSC is 3 μm. Because preparation of the area of electrode materials is extremely small (a few dozen microns) for a miniature supercapacitor, the measured current in the electrochemical test is also extremely small. We therefore frequently use mA/cm 2 and Ω cm 2 in the original manuscript.
To improve the quality of the article, we follow the reviewer's opinion and use ohms to display the internal resistance ( Figure R1.28). This part is revised as following: due to the short diffusion distance of ions, electrolyte ions are placed in the narrow gap between electrodes, which makes it easy to transport and results in higher performance 48 ." This part is revised as following: "The interdigital MSC exhibited the optimal gravimetric capacitance; however, the parallel strip MSC exhibited excellent gravimetric capacitance, higher than the This part is revised as following:

Our Response
We thank the reviewer for their valuable advice, which has been extremely important in improving the quality of the paper.
In our work, the current density of 4 mA/cm 2 is equal to 1.33×10 4 mA/cm 3 or 2857 mA/g, which is relatively high for a miniature thin supercapacitor. Because our MSCs are tens of microns in size and their narrow gap is minute, they can be charged and discharged rapidly at this density. The miniature supercapacitor has its own unique advantages; for example, it can be perfectly matched to numerous niche applications. Although the area and volumetric capacity is higher than that of other supercapacitors, the total amount of capacitance stored is limited due to the small size and area required for miniaturization. Therefore, in the GCD profiles, the charge and discharge times are shorter than for ordinary supercapacitors. We also investigated a large number of studies R1.60-68 on miniature supercapacitors and found the same results.
The charge and discharge times increase when we reduce the current density, reaching approximately 450 s at 1 mA/cm 2 , which demonstrates the excellent performance of our MSCs ( Figure R1.29 (a)).
In Figure   This part is revised as following: This part is revised as following: "GCD curves at 80mV s -1 and 2 mA cm -2 " Fig. 3."

Our Response
We are grateful for your valuable advice which has inspired us to explore further the mechanism of laser reduction of graphene and manganese oxide materials. The purpose of our experiment was to utilize the shaped femtosecond laser to reduce the GO in-situ while simultaneously synthesizing the manganese dioxide complex. The main purpose of our Raman and XPS tests was to demonstrate the reduction effect of GO and the generation of manganese dioxide products. Notably, the nanoparticles of    Since the process of laser-regulated material synthesis is very complex, we should make a comprehensive study and exploration of laser-induced products.
Therefore, XRD tests were added to characterize the composites irradiated by  The XRD patterns of the LIG/Manganese oxides LIG showed peaks that were similar, which can be well indexed to plane of the tetragonal α-MnO 2 structure.
However, we can still find differences through careful observation. The most obvious one is that the peak intensities of the XRD patterns of Laser-210 LIG/Manganese oxide and Laser-250 LIG/Manganese oxide are stronger than others'.

Modifications
The added part is inserted following Page 9, Paragraph 1, Line 1 is as following: "During the SSFL reduction process, the effect of photothermal reduction/oxidation became increasingly apparent as the laser fluence was increased.
By altering the laser fluence, LIG/Manganese oxides were successfully synthesized through photomodulation of the reaction mechanisms (photochemical and photothermal reduction/oxidation). We varied the laser fluence (170-290 mJ cm -2 ) of the SSFL to investigate differences in conductivity and electrochemical characterization and identify the optimal reduction/oxidation effect. The resistance and conductivity of the material reached their minimum and maximum, respectively, when the laser fluence was 210 mJ cm -2 (Supplementary Fig. 7 and 8), which implies that the LIG/Manganese oxides composite has large potential capacitance 43 Fig. 10). The different XRD patterns exhibited similar peaks, which could be all well indexed to plane of the α-MnO 2 structure. However, when the laser fluence was considerably lower or higher than 210 mJ cm -2 , one or two other weak peaks appeared, and the peak intensities in the XRD patterns were lower.
The Raman spectra were extremely similar when the laser fluence was between 170 and 290 mJ cm -2 ( Supplementary Fig. 11). We compared the Raman spectra in three cases-untreated, fs-laser modified, and fs-laser reduced-on the basis of the laser fluence (Fig. 3c). Clear G bands were characteristics of sp 2 hybridized C-C bonds at 1580 cm −1 . D bands of residual oxygen functional groups and other defects 44  The added part is inserted following Page 9, Paragraph 2, Line 6 is as following: "X-ray photoelectron spectroscopy (XPS) was used to assess the difference    Here are some detailed comments:"

Our Response
We appreciate the reviewer's efforts in reviewing our paper. We greatly appreciate your suggestions, and the detailed comments are insightful and critical for improving the manuscript. We are happy to have received such excellent advice for improving the quality of the paper. What's the relationship to achieve "ultra-fast patterning of laser induced graphene/MnO 2 electrodes"? Is it to get better resolution or faster pattern speed?

Reviewer's Comments
More discussion and experimental results should be provided to support the calculation at the beginning of the discussion part."

Our Response
The detailed comments proved helpful in improving our paper. We erred in not clearly expressing the importance of reshaping the femtosecond laser and optimization of the Gerchberg-Saxton (GS) algorithm. We had previously introduced the light field distribution of the shaped beam after SLM and dynamic transformation of high-quality shaped beams in the supplementary materials but we did not discuss it in detail. We have now provided a more detailed discussion of the advantages of shaped femtosecond laser and the optimization of algorithms.
First, we used a spatially shaped femtosecond laser to achieve "ultrafast patterning of laser-induced graphene/MnO 2 electrodes." This innovative technology was used to shape the light field into an arbitrary pattern in space so that it can be used to pattern the complete MSC. "The reason for reshaping the ss-fs laser" was to obtain the patterned light. We implemented this technology to fabricate the MSCs rapidly.
In this way, each single pulse can be achieved a MSC processing. We used the Ti: sapphire laser regenerative amplifier system, it can generate 1,000 single pulses per second, so a single MSC can be fabricated in just 0.001 seconds. The processing efficiency was tens or hundreds of times more efficient than previously reported processes of MSCs R1-6 .   which is time consuming. In our method, the laser was directly changed into a patterned laser and used for processing, and a light field with controllable shape and size was used. Each pulse can achieve complete processing of a supercapacitor, which results in ultrahigh processing efficiency. Reshaping the ss-fs laser can achieve ultrafast patterning of laser-induced graphene/MnO 2 electrodes.
In spatial shaping of the femtosecond laser, an ideal optical field pattern can be designed using the algorithm in advance. Then, we can realize the output of the pattern optical field through SLM. To obtain the best machining effect, we optimized the GS algorithm to achieve a high-quality light field to fabricate a high-resolution MSC rapidly.
The GS algorithm is an iterative optimization algorithm based on Fourier transform. The algorithm can be used to calculate the phase distribution of the hologram to generate arbitrary light intensity distribution in the mirror plane R8 .
The incident light field distribution 0 1 2 ( , ) A i i and initial phase  We continuously modified the amplitude of the desired target light field to accelerate the iteration process and improve uniformity. To obtain a high-quality light field, we set the cycle coefficient such that the number of iterations of the algorithm increased.    Using the aforementioned conditions, we could process 3,000 MSCs in 1 min.
This rate is tens or hundreds of times more efficient than that of previously reported processes of MSCs R1-6 . The manufacturing efficiency, size, and narrow gap of our strategy were compared with those of previously reported methods.

Modifications
According to the comments of the reviewer, we have revised the involved part The original part form Page 4, Paragraph 2, Line 1to Line 19 is as flowing: "Manufactured technology for L-S-MSCs via SFLS strategy. We constructed a complete processing system for flexible and polymorphic L-S-MSCs (Fig. 1), the ss-fs laser beam was processed into the graphene oxide (GO) hybrid film after being reshaped by spatial light modulator. In advance, we used improved GS algorithm to generate recognizable phases through the formula:   Supplementary Information 1.3. We used the optimized algorithm regulate the optical field region, in which the beam width and z-axis propagation distance represent the basic parameters of a three-dimensional optical field. We can arbitrarily change the parameter design to control the size of the optical field, and a fixed depth for the 3D processing within a certain range. Since the SSFL has a uniform light field on each plane in the z-axis direction, excellent 3D reduction can be achieved in the processing of GO hybrid film. Fig. 1a reveals that the original Gaussian beam was transformed into a phase pattern after being reshaped and then transmitted by a 4f relay system. This approach can avoid the loss of light in the transmission path 27 and achieve excellent processing results." The corresponding content added in Supporting Information is as following:

Optimization of the Gerchberg-Saxton (GS) algorithm
In spatial shaping of the femtosecond laser, an ideal optical field pattern can be designed using the algorithm in advance. Then, we can realize the output of the pattern optical field through SLM. To obtain the best machining effect, we optimized the GS algorithm to achieve a high-quality light field to fabricate a high-resolution substituted for the amplitude calculated in the previous step, and the phase was kept unchanged to obtain the object square light field. Finally, the iteration was repeated until the target light field whose amplitude distribution satisfied the requirements was obtained.
On this basis, we dynamically regulate the amplitude of the target light field.
Firstly, we calculated the difference between the average amplitude obtained by the Fourier transform and the target amplitude, as  We conclude that optimizing the GS algorithm results in a superior resolution optical field distribution. Figure R2 depicts the optical field distribution diagram optimized by the algorithm. The spatially shaped femtosecond laser can be used to directly pattern the hybrid GO film on MSCs. Furthermore, such a spatially shaped laser can be used to fabricate high-resolution MSCs in a very short time. We used the Ti: sapphire laser regenerative amplifier system, which can generate 1,000 single pulses per second. In theory, a single MSC could be fabricated in only 1 millisecond. The actual processing speed observed was more than 3,000/min, which is tens or hundreds of times more efficient than previously reported processes for fabricating MSCs [31][32][33][34][35][36] . The SSFL also has the advantages of high machining accuracy and near faultless processing consistency, enabling rapid and large-scale application.
As illustrated in the Table,  showed random curved gap channels. The evidence to prove that the high resolution of "500 nm" has been achieved is insufficient."

Our Response
We thank the reviewer for the efforts in reviewing our paper. In our study, the spot of the femtosecond laser is not a traditional Gaussian beam. As mentioned in the previous response, the femtosecond laser can be used to reshape the patterned light field in space.
The spot size of the single femtosecond laser pulse in our study could be adjusted from 15 × 15 to 100 × 100 μm 2 . Furthermore, the narrow gap could be adjusted by designing different light fields. As mentioned earlier, we used the Ti:sapphire laser regenerative amplifier system because it can generate 1,000 single pulses per second.
Therefore, in theory, a single MSC could be fabricated in just 0.001 s.
In practice, we fabricated more than 50 MSCs per second. Different sizes of MSCs were fabricated in one step by changing the spot size. To achieve a superior display, we fabricated MSCs of different sizes. As depicted in Figure R2.5 a-c, we could prepare MSCs ranging from 15 × 15 to 100 × 100 μm 2 in a short time. These capacitors can maintain regular shapes.  Notably, 500 nm is the highest resolution achieved in the processing of MSCs in this study for the convenience of subsequent electrochemical testing and studies considering light field interference. Our processing resolution was realized through the pattern design of the light field shape. Thus, the slit between design patterns was used to achieve the highest resolution.
To demonstrate the high-resolution fabrication ability of our technology, we patterned simple-shaped MSCs ( Figure R2.7). We patterned parallel strip-shaped MSCs with different narrow gaps to achieve a straight line gap. In Figure R2.7, the resolution of the slit is less than 500 nm and is even close to 350 nm in some parts. We achieved a high resolution through the pattern design of the light field shape.
Thus, the slit between design patterns was used to achieve the highest resolution, which was not limited by the laser wavelength. Therefore, a 3D reduction could be achieved using the 3D shaped laser. To demonstrate the machining resolution of our technology, we performed high-resolution experiments using SSFL. We designed a two-ringed MSC with a light field distribution as depicted in Figure R2.8 (a).
High-resolution patterning was realized by adjusting the narrow gap between the two rings. Figure R2.8 (b) illustrates the SEM images of the patterns with different narrow gaps. The minimum resolution of the slit was achieved at the junction of two rings.
The narrow gap can be designed with the laser. We achieved an ultrasmall narrow gap of 11.6 nm, which is beyond the limit of traditional diffraction. Nanometer precision benefits from the design of light fields.

Modifications
According to the comments of the reviewer, we have revised the involved part The original part form Page 7, Paragraph 1, Line 13 to Line 18 is as flowing: "L-S-MSCs of various shapes are in the tens to hundreds of micrometers in length. In such a machining precision, our technology has obtained a satisfactory machining effect. Supplementary Fig. 2 clearly displays the regular electrode morphology. The spacing could be adjusted by designing different light field, and the narrow gap of the L-S-MSCs is only 500 nm (Supplementary Fig. 3). The varying sizes can be controlled by designable light fields from 15×15 μm 2 to 100×100 μm 2 ( Supplementary Fig. 4)." This part is revised as following: "The shape of the spot could be designed, and the size of the spot could be regulated by transforming the target light field. The size of the spot determined the size of the entire MSC, because the MSCs of various shapes were patterned using the SSFL in one step. The varying sizes can be controlled by designable laser spots from 15×15 μm 2 to 100×100 μm 2 ( Supplementary Fig. 3). We could transform Gaussian light into shaped light to form the patterned light spots and use the SSFL to extrude the narrow gap of patterns that could break the diffraction limit. MSCs with different narrow gaps could be fabricated by designing different light fields, and a MSC with a narrow gap of 500 nm was fabricated using SSFL on a GO hybrid film ( Supplementary Fig. 4). These findings indicate that our method achieved extremely high processing efficiency while maintaining high processing accuracy." The corresponding content added in Supporting Information is as following:

μm, and (c) 1 μm).
To demonstrate the high-resolution fabrication of our technology, we patterned a simply shaped MSC to demonstrate the higher resolution of the electrode gaps. We patterned parallel strip-shaped MSCs with different narrow gaps so that the gap is a straight line and is clearer to see. As shown, the resolution of the slit is less than 500 nm, and close to 350 nm in some parts. Our resolution was realized through the pattern design of light field shaping, where the slit between design patterns was used to achieve the highest resolution but was not limited by the laser wavelength. This potentially explains how to complete a 3D reduction using the 3D shaped laser."    Since the process of laser-regulated material synthesis is very complex, we should make a comprehensive study and exploration of laser-induced products.

"The physicochemical characterization of the laser induced LIG
Therefore, XRD tests were added to characterize the composites irradiated by  The XRD patterns of the LIG/Manganese oxides LIG showed peaks that were similar, which can be well indexed to plane of the tetragonal α-MnO 2 structure.
However, we can still find differences through careful observation. The most obvious one is that the peak intensities of the XRD patterns of Laser-210 LIG/Manganese oxide and Laser-250 LIG/Manganese oxide are stronger than others'.

Modifications
The added part is inserted following Page 9, Paragraph 1, Line 1 is as following: "During the SSFL reduction process, the effect of photothermal reduction/oxidation became increasingly apparent as the laser fluence was increased.
By altering the laser fluence, LIG/Manganese oxides were successfully synthesized through photomodulation of the reaction mechanisms (photochemical and photothermal reduction/oxidation). We varied the laser fluence (170-290 mJ cm -2 ) of the SSFL to investigate differences in conductivity and electrochemical characterization and identify the optimal reduction/oxidation effect. The resistance and conductivity of the material reached their minimum and maximum, respectively, when the laser fluence was 210 mJ cm -2 (Supplementary Fig. 7 and 8), which implies that the LIG/Manganese oxides composite has large potential capacitance 43 Fig. 10). The different XRD patterns exhibited similar peaks, which could be all well indexed to plane of the α-MnO 2 structure. However, when the laser fluence was considerably lower or higher than 210 mJ cm -2 , one or two other weak peaks appeared, and the peak intensities in the XRD patterns were lower.
The Raman spectra were extremely similar when the laser fluence was between 170 and 290 mJ cm -2 ( Supplementary Fig. 11). We compared the Raman spectra in three cases-untreated, fs-laser modified, and fs-laser reduced-on the basis of the laser fluence (Fig. 3c). Clear G bands were characteristics of sp 2 hybridized C-C bonds at The added part is inserted following Page 9, Paragraph 2, Line 6 is as following: "X-ray photoelectron spectroscopy (XPS) was used to assess the difference before ( Supplementary Fig.12) versus after SSFL ablation under a laser fluence of 210 mJ cm -2 ( Fig. 3d-f). The C 1s spectrum consisted of three peaks: C-C/C=C (284.

"Although the laser induced fabrication of metal oxides is not new, the authors should provide more details about the mechanism(s) related to the transition from
Mn 2+ to MnO 2 ."

Our Response
The detailed comments are valuable. We thank the reviewer for providing advice to improve the paper's quality.
Laser radiation is characterized by its highly coherent, responsive, and intense nature. Furthermore, laser radiation can be delivered in short pulses R12 . In particular, the femtosecond laser has ultrahigh peak powers (>10 13  We proposed a photosynthetic method for synthesizing LIG-MnO 2 . Figure   R2.13 illustrate the physics and chemical mechanisms of GO reduction and MnO 2 . The high power of the shaped femtosecond laser we used was sufficient to irradiate GO at a local scale many times. This process also resulted in the photothermal reduction of GO and a porous graphene structure.
We proposed a novel photosynthetic mechanism for synthesizing LIG-MnO 2 . In this mechanism, Mn 2+ to MnO 2 transitions facilitates the reduction of GO to LIG. GO provides not only the energy required for Mn 2+ oxidation but also a strong attachment point for MnO 2 . Thus, high-quality MnO 2 nanoparticles were fabricated and doped with LIG to form a composite material with a firm structure.

Modifications
According to the comments of the reviewer, we have revised the corresponding part in our manuscript.
Therefore, the SSFL reduction in the experiment was caused by the combined effect of photochemical and photothermal reactions. Our findings indicated that gas was released when the SSFL reduced GO composite film, which is crucial in the formation of 3D porous structure composites. The 3D porous patterned structure fabricated in one step using the SSFL employed graphene as a solid skeleton, and the uniform effect of the light field enabled manganese dioxide nanoparticles to be evenly distributed on the graphene skeleton. The pores functioned as shortcuts for rapid ion diffusion between graphene layers, which increased the speed of ion transport across the compressed film. The 3D porous scaffold was very stable, which would mitigate mechanical stress within the electrode and thus ensure the stability of long-term cycling of electrochemical energy storage systems 41,42 . Therefore, the LIG/MnO 2 composite had improved capacitance." The original part in Page 9, Paragraph 1: "Analytical characterization of the LIG/MnO 2 . Fig. 3a  The added part is inserted following Page 9, Paragraph 1, Line 1 is as following: "During the SSFL reduction process, the effect of photothermal reduction/oxidation became increasingly apparent as the laser fluence was increased.
By altering the laser fluence, LIG/Manganese oxides were successfully synthesized through photomodulation of the reaction mechanisms (photochemical and photothermal reduction/oxidation). We varied the laser fluence (170-290 mJ cm -2 ) of the SSFL to investigate differences in conductivity and electrochemical characterization and identify the optimal reduction/oxidation effect. The resistance and conductivity of the material reached their minimum and maximum, respectively, when the laser fluence was 210 mJ cm -2 (Supplementary Fig. 7 and 8), which implies that the LIG/Manganese oxides composite has large potential capacitance 43 Fig. 10). The different XRD patterns exhibited similar peaks, which could be all well indexed to plane of the α-MnO 2 structure. However, when the laser fluence was considerably lower or higher than 210 mJ cm -2 , one or two other weak peaks appeared, and the peak intensities in the XRD patterns were lower.
The Raman spectra were extremely similar when the laser fluence was between 170 and 290 mJ cm -2 ( Supplementary Fig. 11). We compared the Raman spectra in three cases-untreated, fs-laser modified, and fs-laser reduced-on the basis of the laser fluence (Fig. 3c). Clear G bands were characteristics of sp 2 hybridized C-C bonds at The added part is inserted following Page 9, Paragraph 2, Line 6 is as following: "X-ray photoelectron spectroscopy (XPS) was used to assess the difference before ( Supplementary Fig.12) versus after SSFL ablation under a laser fluence of 210 mJ cm -2 (Fig. 3d-f). The C 1s spectrum consisted of three peaks:

"The conductivity of 3.2 S m -1 of the laser induced graphene is moderate.
However, for the MSC, the measured time constant of 10.6 μs, is extremely short time.
The author should provide more explanation about how such a fast time constant is possible with such relatively poor conductivity."

Our Response
We truly appreciate the reviewer's suggestion regarding conductivity and time constants. The reviewer's valuable advice is crucial for improving the quality of the paper.
The theoretical conductivity of monolayer graphene materials is high, which is a crucial concern in electrochemical devices. However, GO material has poor electrical conductivity. Therefore, GO films are reduced to LIG films to improve electrical μm × 100 μm, and the probes were placed 80 μm apart. Bulk conductivity was evaluated using the following equation: where R is the resistance for the voltage current plots (Supplementary material), I is the distance between the probe tips (80 μm), and A is the cross-sectional area of the pattern (100 μm × 3 μm). By measuring the bulk conductivity as a reference, we obtained the optimal selection of laser parameters by conducting experiments.  In our study, deoxidization and reduction of GO produced a gas, which subsequently formed a 3D porous structure. The porous laser-induced graphene/MnO 2 with a large specific surface area and multiple paths facilitated ion transmission in the electrodes. These pores functioned as shortcuts for rapid ion diffusion between graphene layers and increased the speed of ion transport across the compressed film.
As depicted in Figure R2.15, the porous structure provided a fast path for ion transfer, which enabled effective ion contact with the electrode material. This ensured rapid charging and discharging. Therefore, our MSCs exhibited an ultrashort time response (10.6 μs).

Modifications
According to the comments of the reviewer, we have revised the corresponding part in our manuscript.
The original part in Page 13, Paragraph 1, Line 1 to 5, the detail is as following: "To discover the optimal reduction effect, we changed laser fluence to explore the difference in conductivity and electrochemical characterization. Supplementary  9). Other studies 47 have suggested that measurements report the bulk conductivity and not the surface conductivity, due to our hybrid film being very thin, the calculated conductivity compared with traditional techniques was probably underestimated. To further explore the effects of laser fluence on materials, we performed Raman spectroscopy and the electrochemical performance of LIG/MnO 2 L-S-MSCs processed in different laser fluence (Supplementary Fig. 10). Coincidentally, the laser fluence of the best conductivity, the most obvious Raman characteristic peak and the highest area specific capacitance of the L-S-MSCs ( Supplementary Fig. 11) were all at 210 mJ cm -2 . The reason might be that in microelectronic devices, the L-S-MSCs with excellent electrical conductivity can achieve higher capacitance characteristics because of the rapid transfer of charge." These parts are revised as following: "During the SSFL reduction process, the effect of photothermal reduction/oxidation became increasingly apparent as the laser fluence was increased.
By altering the laser fluence, LIG/Manganese oxides were successfully synthesized through photomodulation of the reaction mechanisms (photochemical and photothermal reduction/oxidation). We varied the laser fluence (170-290 mJ cm -2 ) of the SSFL to investigate differences in conductivity and electrochemical characterization and identify the optimal reduction/oxidation effect. The resistance and conductivity of the material reached their minimum and maximum, respectively, when the laser fluence was 210 mJ cm -2 (Supplementary Fig. 7 and 8), which implies that the LIG/Manganese oxides composite has large potential capacitance 43 Fig. 10). The different XRD patterns exhibited similar peaks, which could be all well indexed to plane of the α-MnO 2 structure. However, when the laser fluence was considerably lower or higher than 210 mJ cm -2 , one or two other weak peaks appeared, and the peak intensities in the XRD patterns were lower.
The Raman spectra were extremely similar when the laser fluence was between 170 and 290 mJ cm -2 ( Supplementary Fig. 11). We compared the Raman spectra in three cases-untreated, fs-laser modified, and fs-laser reduced-on the basis of the laser fluence (Fig. 3c). Clear G bands were characteristics of sp 2 hybridized C-C bonds at The porous structure provided a faster path and more path choices for the ion transfer.
This enabled the ions to contact the electrode material quickly and fully, thus charging and discharging more quickly. This ability to optimize charge transport is shown in Nyquist plots and Bode plots. Our MSCs exhibited an ultra-small time response (0.01 ms) and low equivalent series resistance (0.85 mΩ/cm 2 ).

"More details about the dimensional parameters, such as the interdigital gap
width and the electrode and device dimensions, should be provided in the device electrochemical performance discussion. These parameters can critically affect electrochemical performance."

Our Response
Thank for your detailed comments regarding the manuscript. They have proved valuable for improving our paper.
We studied the parameters of different shapes of MSCs and the laser fluence during processing. However, these parameters are not sufficient, and more parameters should be researched to understand the chemical performance of MSCs. As recommended by the reviewer, we performed experiments on the interdigital gap width of the electrode, device dimensions, and thickness of the MSC.
(1) We explored the effect of the interdigital gap width on electrochemical performance when designing the MSCs with narrow gaps of 500 nm and 2, 4, and 6 μm ( Figure R2.16).  The narrower the gaps of electrodes are, the faster ion transfer and charge and discharge are, which considerably contributes to electrochemical performance. In the actual measurement, a gap of a few hundred nanometers can cause collision losses of electrode materials, which affects charge transfer and electrochemical performance.
The electrochemical performance of MSCs with different narrow gap was plotted against various scan rates ( Figure R2.18). The results of our experiments revealed that MSCs with different narrow gaps differences from the areal capacitance in the case of a lower scan rate. When the narrow gap was 2 μm, the highest areal capacitance was 67 mF cm −2 . The areal capacitance was 62, 58, and 51 mF cm −2 at the corresponding gaps of 4 μm, 500 nm, and 6 μm. We evaluated the electrochemical behavior of MSC at different scan rates. Figure   R2.19 depicts the CV curves at low and high scan rates of the MSCs with different device dimensions. Notably, the areal capacitances of different device dimensions were close at high or low scan rates. An areal capacitance of 38 mF cm −2 was achieved at 80 mV s −1 when the device dimension was 50 × 50 μm 2 , which was slightly higher than that when device dimensions were 15 × 15 and 100 × 100 μm 2 (37 and 35, respectively). When the scan rate was increased to 800 mV s −1 , the areal capacitance for all the dimensions was almost the same (18 mF cm −2 ).      CV curves were recorded at variable scan rates to evaluate the effect of different microscale interdigital narrow gaps in the MSCs. As shown, the CVs of the high-resolution MSCs maintained a rectangular shape at different scan rates. When the interdigital narrow gaps were 500 nm, 2 μm, 4 μm, and 6 μm, different electrochemical performances are obtained. Of these, the MSCs with a narrow gap of 2 μm exhibited the optimal electrochemical performance, slightly higher than that with a gap of 500 nm and higher than those with gaps of 4 and 6 μm. of MSCs. To increase the accuracy of the measurements, we simultaneously measured the size of a dozen micron miniature supercapacitor requirements. We customized a probe with a contact diameter of 3 μm for use with a 100× confocal microscopy system. CV curves are shown at low and high scan rates for MSCs with different device dimensions. Contrary to expectations, the areal capacitances of different device dimensions were extremely similar at high or low scan rates. An areal capacitance of 38 mF/cm 2 was achieved at 80 mV/s when the device dimension was 50 × 50 μm 2 , which was slightly higher than the areal capacitances of 37 and 35 mF/cm 2 achieved when the device dimensions were 15 × 15 μm 2 and 100 × 100 μm 2 , respectively.

Supplementary
When the scan rate was increased to 800 mV/s, the areal capacitance was almost the same (18 mF/cm 2 ). showed that the dimensions of the MSC had an effect on the electrochemical performance at low scan rates, but this was almost negligible at high scan rates.

Supplementary
However, the MSC with dimensions of 50 × 50 μm 2 exhibited uniformly good electrochemical performance at both high and low scan rates.  Specifically, at a low scan rate, the volumetric capacitance of a MSC with a thickness of 3 μm is slightly higher than that of the other MSCs. At a high scan rate, the supercapacitor with a thickness of 1 μm has the advantage. Figure 3 n and o or the indicated lattice spacings (0.29 nm and 0.33 nm) in these two TEM images are incorrect."

Our Response
We sincerely thank the reviewer for their patient review and valuable suggestions. We are very sorry for our oversight. We submitted the original TEM image to the system and used professional measurement software to resize the lattice spacing. Furthermore, we also evaluated other TEM and SEM graphs in the paper.
Thank you for your meticulous reading and kind reminder.
We agree that the scale bars in Figure 3 were incorrect in the original manuscript.
We used the aforementioned program to measure the correct lattice spacing, but erred in reading the scale bars. Therefore, we replaced the TEM image in the source data, remeasured the lattice distance and relabeled the scale.

Modifications
We have revised the corresponding part in our manuscript as per the reviewer's suggestions Figure 3 in manuscript was replaced.

"The English in this manuscript, especially the materials characterization
discussion and electrochemical performance evaluation could be further improved by a professional English polishing service team. There are still some typos that need further revision before submission to another journal, such as "surfacearea" on page 2."

Our Response
We deeply admire the reviewer's professional perspective on the paper. Your suggestion helped us to considerably improve the quality of the article and avoid mistakes.
All of our coauthors rewrote the manuscript to improve its fluency and readability. We then sent the article to a professional English editing service team to improve the language and grammar of the article. We have emphasized material characterization and electrochemical performance evaluation.
Thank you again for your patient review and valuable comments. given as appended below.

Our Response
We truly appreciate the reviewer for the efforts for reviewing our paper. We are happy to have received the following excellent suggestions for improving the paper quality. We have modified the corresponding text following the reviewer's comments.

"I have a crucial comment on the title of this paper. What does ultrafast
signify? Is it a very fast method or the authors used ultrafast laser sources? Clarify."

Our Response
We are very grateful for the reviewer's detailed comments, which were crucial for improving our paper.
We apologize for the misunderstanding caused by the unclear expression. We think the comment on the title is meaningful; hence, the title has been revised. We want to emphasize the very fast processing method (the femtosecond laser we used is indeed an ultrafast laser) in the title. In the title of the original manuscript, "Ultrafast laser-stamping for MSC manufacturing," the term "ultrafast" is really ambiguous. In combination with the comment that "Manufacturing technology is not the proper phrase for this manuscript," all coauthors have made rigorous and accurate changes to the title.

Modifications
According to the reviewer's comments, we have revised the corresponding part in our manuscript.
The original title is as follows: "Ultrafast laser-stamping for MSCs manufacturing" The title is revised as following: "Laser photonic-reduction stamping for graphene-based MSCs ultrafast fabrication"

"
If it is the very fast production of the device, then one has to justify with literature and explain with the statement '1 cm2 within 10 minutes', which is not a fast procedure."

Our Response
We thank the reviewer for the detailed and thorough attention to the paper and the advice for improving the paper quality. However, our description in the article was unclear and could cause misunderstanding. In the revised manuscript, we have mentioned that the processing time of 10 min was only to form a specific concept of our technology, ">30,000 laser-stamping MSCs of 1 cm 2 were produced within 10 min," to reflect the capacity of ultrafast processing and micro integration.
The recent technological trend of using electronic devices has increased the requirement of micro power sources and small-scale energy storage devices R1-3 .
Therefore, we must minimize the size of single supercapacitors to integrate multiple supercapacitors into the smallest possible area. The size of an average miniature supercapacitor is mostly in the centimeter range, and the minimum distance between adjacent electrodes in an interdigitated configuration ranges from 500 to 5 μm R4-18 . In our study, we realized the ultrafast fabrication of supercapacitors with a minimum size (15 × 15 μm 2 ) and high resolution (500 nm). We integrated >30,000 MSCs of this size into a considerably small area (1 cm 2 ).
To demonstrate our technology more intuitively, Figures R3.1 and 2 illustrate the difference between the laser direct writing and our shaped-laser processing of MSCs.  Thus, "considerably rapid device production" implies that we can fabricate tens of thousands of MSCs within 10 min. We used the Ti:sapphire laser regenerative amplifier system, and it can generate 1,000 single pulses per second. In theory, each single pulse can be achieved through MSC processing; consequently, a single MSC can be fabricated in only 0.001 s. During actual processing, we processed >50 MSCs per second. As the below table shows, our technology is ten or hundred times more efficient than the reported processes of MSCs R18-23 .

Electrochemical activation 22 1×1 cm 2
Microwave radiation 23 1×2 cm 2 SFLS strategy (Our work) 50×50 μm 2 (0.5 μm) We apologize for the misguiding statement of "1 cm 2 within 10 minutes." In fact, completing processing of >30,000 supercapacitors in 10 min is considerably rare, and for a size of a dozen microns of supercapacitors, 1 cm 2 is a relatively large area. In this case, we are not emphasizing the relationship between 10 min and 1 cm 2 . The statement emphasizes that numerous MSCs can be prepared in a considerably short time and small area, which is highly crucial for the practical applications of energy storage in microdevices. To show our super-high processing efficiency to readers in a more specific and digital way, we used "10 min" as a measure of time required to process >30,000 supercapacitors. Therefore, "10 min" is just an expression used for a specific description, and "1 cm 2 " is used to represent the substantially small area required for accommodating numerous MSCs, thereby emphasizing the advantages of our miniaturized preparation.
This confusing expression has been revised in the article.

Methods
Size of supercapacitors (narrow gap) Fabrication efficiency /30min According to the reviewer's comments, we have revised the corresponding part in our manuscript to better describe the ultrahigh efficiency of this technology without causing misunderstanding.
The original abstract form Page 1, Paragraph 1, Line 3 to Line 6 is as flowing: "Here, a versatile spatially shaped femtosecond laser stamp strategy is proposed to ultrafastly manufacture the designable flexible laser-stamping MSCs from the graphene oxide based film. More than 30,000 laser-stamping MSCs are produced in 1 cm 2 within 10 minutes." This part is revised as following: "Here, a flexible, designable MSC can be fabricated by a single pulse laser photonic-reduction stamping. A thousand spatially shaped laser pulses can be generated in one second, and over 30,000 MSCs are produced within 10 minutes." The original part form Page 6, Paragraph 1, Line 1to Line 9 is as flowing: "The ss-fs laser can achieve ultra-fast fabrication of various-shapes L-S-MSCs (Fig.   1b). Notably, such high fabrication efficiency for flexible L-S-MSCs is rare, and ss-fs laser also demonstrates high machining accuracy and near faultless processing consistency, which enable rapid and large-scale applications. Under present conditions, we could process 3,000 L-S-MSCs in 1 minute. This rate was tens or hundreds of times more efficient than previously reported processes of MSCs [28][29][30][31][32][33] . As the Table   shows, our SFLS strategy is compared with the methods that have been reported before in manufacturing efficiency, size and narrow gap. The technology we proposed has unprecedented manufacturing efficiency and could fabricate 90,000 L-S-MSCs in thirty minutes. Our processing video is included in the Supplementary Information." This part is revised as following: "The SSFL method achieved ultrafast fabrication of variously shaped MSCs (Fig.   1b) and revolutionizes the traditional processing method of direct laser writing ( Supplementary Fig. 1). Traditional laser point-by-point writing of the focal spot is realized by controlling the movement of the translation stage, which considerably limits the method' s application in the ultrafast fabrication of MSCs. In our work, the spot of each laser pulse can be a designable pattern spot shaped by a spatial light modulator that directly and instantaneously completes a patterned MSC. The SSFL strategy not only retains the advantages of being mask-free, flexibility and high-resolution, it also achieves the ultrafast fabrication of MSCs.
We used the Ti: sapphire laser regenerative amplifier system, which can generate 1,000 single pulses per second. In theory, a single MSC could be fabricated in only 1 millisecond. The actual processing speed observed was more than 3,000/min, which is tens or hundreds of times more efficient than previously reported processes for fabricating MSCs [31][32][33][34][35][36] . The SSFL also has the advantages of high machining accuracy and near faultless processing consistency, enabling rapid and large-scale application.
As illustrated in the Table,  multipatterned rapid processing is difficult to achieve. The incident beams (Gaussian beams) were transformed into arbitrary geometric target beams in SLM by programming phase patterns; the shaped beams were then transmitted on the hybrid GO films. The shaped femtosecond laser can be formed in one step and alters the shape by changing the phase pattern. The spot of the shaped laser is a designable pattern that can directly and instantaneously complete patterned MSCs. In conjunction with the advantages of laser direct writing, this technology greatly improves processing efficiency and achieves consistency for large-area processing. In theory, this process is instantaneous.
The added part is inserted following Page 8, Paragraph 1, Line 1 is as following: "Notably, the proposed technique can fabricate numerous MSCs within an extremely short time and small area, which is particularly valuable for the practical application of energy storage in microdevices and can be widely extended to other material systems, or other graphene-based composites."

Reviewer's Comments
3.3. "Several optimization parameters are missing. e.g. spot size and speed of the laser or the film quality and how it is changing during that optimization."

Our Response
We thank the reviewer for their careful review of our paper. We are grateful to receive such excellent advice to improve our paper quality.
We studied the parameters of different shapes of microcapacitors and different laser fluences during processing. However, these parameters were not enough to further discuss the influence of many parameters on the chemical performance of MSCs. According to the reviewer's suggestions, we performed an experiment of parameters of the spot size and the narrow gap between the spot and film quality of MSCs.
(1) The spot size is a vital parameter in the preparation of our MSC. We employed spatial light field shaping to transform the original Gaussian light beam into a three-dimension-shaped laser. This laser was patterned in one step in the form of a single pulse without direct laser writing. Laser direct writing requires a program-controlled continuous laser scan of focused spots to complete one pattern R24-26 , which makes MSC preparation a time-consuming procedure. In our method, the laser is directly changed into a pattern laser that can be used for processing, and the light spot focused on a single point is changed to a shaped light field with a controllable shape and size. We used the Ti:sapphire laser regenerative amplifier system that can generate 1,000 single pulses per second. Therefore, the laser speed for fabrication was fixed.
Each single pulse can achieve MSC processing; consequently, a single MSC can be fabricated in only 0.001 s. During actual processing, we processed >50 MSCs per second. The processing efficiency obtained using this method is considerably high.
Reshaping the femtosecond laser can provide "ultrafast patterning of laser-induced graphene/MnO 2 electrodes." The laser spots of our shaped laser are shown in the following figure.  We evaluated the electrochemical behavior of MSC at different scan rates. Figure   R3.5 depicts the CV curves at low and high scan rates of the MSCs with different device dimensions. Notably, the areal capacitances of different device dimensions were close at high or low scan rates. An areal capacitance of 38 mF cm −2 was achieved at 80 mV s −1 when the device dimension was 50 × 50 μm 2 , which was slightly higher than that when device dimensions were 15 × 15 and 100 × 100 μm 2 (37 and 35, respectively). When the scan rate was increased to 800 mV s −1 , the areal capacitance for all the dimensions was almost the same (18 mF cm −2 ).   (2) We explored the effect of the interdigital gap width on electrochemical performance when designing the MSCs with narrow gaps of 500 nm and 2, 4, and 6 μm ( Figure R3.7).   The results of our experiments revealed that MSCs with different narrow gaps differences from the areal capacitance in the case of a lower scan rate. When the narrow gap was 2 μm, the highest areal capacitance was 67 mF cm −2 . The areal capacitance was 62, 58, and 51 mF cm −2 at the corresponding gaps of 4 μm, 500 nm, and 6 μm.    The shaped femtosecond laser can be formed in one step, and shapes can be changed by changing phase patterns. The spot of the shaped laser is a designable pattern spot that can directly and instantaneously achieve the fabrication of patterned MSCs. In addition to the advantages of laser direct writing, this technology considerably improves processing efficiency and can enable the consistency of large-area processing. In theory, this process is completed in an instant.
Therefore, in our processing, changing the speed of laser scanning to influence the processing effect is not required. The whole process is completed in 0.001 s. Thus, the "speed of the laser" in our experiment is equivalent to the speed of laser patterning, which is considerably rapid and stable.

Modifications
According to the comments of the reviewer, we have added the impact of parameters on electrochemical performance.
The added part is inserted following Page 16, Paragraph 3, Line 2 is as following: "On the basis of our findings, we selected the optimal parameter configuration of the interdigital MSCs for further electrochemical tests. We performed a series of parameter research and optimizations for the interdigital MSCs. We investigated the interdigital gap width, device dimensions, and thickness of the MSCs (Supplementary 21-23) to explore the effects of these factors on electrochemical performance." The corresponding content added in Supporting Information is as following:  Specifically, at a low scan rate, the volumetric capacitance of a MSC with a thickness of 3 μm is slightly higher than that of the other MSCs. At a high scan rate, the supercapacitor with a thickness of 1 μm has the advantage.

Our Response
We thank the reviewer for carefully checking the paper in detail and for the suggestion to improve the paper quality. Especially in terms of the professional vocabulary grasp, which highly beneficial us, but also allows us have a more rigorous attitude toward scientific words.
Because of the reviewer's reminder, we realized that "manufacturing technology" is really not a proper phrase for this manuscript. According to the Oxford dictionary, "manufacture" means the making of articles on a large scale using machinery. This is contrary to the central idea of our manuscript.
As the reviewer indicated, our study is actually narrowing down the device geometry and area rather than focusing on bulk-scale production. We prefer to emphasize our innovative proposal of a microfabrication technique that enables ultrafast fabrication of microelectronic devices. We apologize for the misuse of this word. We have revised the word "manufacturing technology" in the revised manuscript. Microfabrication may be an appropriate word choice and may highlight the innovation of our study. Simultaneously, this word provides readers a clear understanding of this novel ultra-efficient technology proposed for the micro-nano field.

Modifications
According to the reviewer's comments, we have revised the corresponding part in our manuscript.
The original title is as follows: "Ultrafast laser-stamping for MSCs manufacturing" The title is revised as following: "Laser photonic-reduction stamping for graphene-based MSCs ultrafast fabrication" The original part in Page2, Paragraph 2, Line 5, the detail is as following: "the manufacturing accuracy" This part is revised as following: "the fabrication accuracy" The original part in Page2, Paragraph 2, Line 10, the detail is as following: "the manufacturing efficiency" This part is revised as following: "the fabrication efficiency" The original part in Page4, Paragraph 2, Line 1, the detail is as following: "manufactured technology for L-SLMSCs via SFLS strategy" This part is revised as following: "Micro fabrication of the MSCs via SSFL" The original part in the Table in Page 6 is as following: "manufacturing" This part is revised as following: "fabrication"

"In my opinion, this work is actually narrowing down the device geometry
and area rather focusing the bulk scale production. In this respect, I am curious to know about the gravimetric capacitance and volumetric capacitance, which an Industry may look into it.

Our Response
The detailed comments are very helpful and greatly valued. We thank the reviewer for the suggestion for improving the paper quality.
The reviewer's suggestions regarding the industrial application of our MSCs are very meaningful, and we have incorporated the industrial applications of our technology in the manuscript. Therefore, providing a highly accurate evaluation of the gravimetric and volumetric capacitance in this manuscript is necessary. According to the reviewer's comments, we carefully studied the gravimetric and volumetric capacitance of MSCs through experiments. Simultaneously, we maintained a similar area of devices and compared the gravimetric capacitance during shape versatility optimization.
(1) Volumetric capacitance of the MSCs fabricated using a shaped femtosecond laser. We selected three typical MSC shapes-concentric circle, parallel strip, and interdigital-and tested their volumetric capacitance. Figure R3.12 reveals the cyclic voltammetry (CV) curves of different patterns acquired at different scan rates.
Irrespective of high and low scan rates, the three types of MSCs with different shapes maintained rectangular CV curves under a voltage window of 0.5 V, proving that the capacitance of the MSCs processed through our strategy is considerably excellent. By contrast, concentric circle-shaped and interdigital MSCs exhibited more regular rectangular curves than parallel strip-shaped MSCs did.  Figure R3.13 presents the volumetric capacitance of versatile-shaped MSCs at diverse scan rates: interdigital MSCs always exhibit a high volumetric capacitance.
The volumetric capacitance of the interdigital MSCs is 131 F cm −3 , which is higher than that of the parallel strip (110 F cm −3 ) and concentric circle (116 F cm −3 ) MSCs.
We concluded that our MSCs were probably micron-scaled, and efficient ion and charge transfer between electrode materials and electrolyte solutions were crucial. In interdigital MSCs, the electrode material area and volume highly were efficiently employed, and the contact area between electrode material and electrolyte was increased; because of the short diffusion distance between ions, electrolyte ions are placed in a narrow gap between electrodes, which makes its transportation easy and results in higher performance R27 . Furthermore, to demonstrate the excellent volumetric capacitance of interdigital MSCs, we tested CV curves under high voltage windows. We found that they could maintain the rectangular shape under a voltage window of 2 V, and they provided ultrahigh volumetric capacitances ( Figure R11).  According to the reviewer's comments, "different areas will contribute to different mass loading of devices; therefore, we must maintain a similar area of devices and compare the gravimetric capacitance during shape versatility optimization." As aforementioned, we normalized the area to study the effect of shapes on the electrochemical capacitance. Therefore, we have presented the  where e m is the effective electrode mass, t m is the total mass in the range area, e S is area of the effective electrode material, t S is the area of the normalized area, ρ is the density of the film of the electrode, h is the thickness of the film. We prepared tens of thousands of MSCs by using quantitative electrode material.
According to the mass ratio of different shapes, we can accurately calculate the mass loading of a single MSC of each shape and obtain the gravimetric capacitance. , and its gravimetric capacitance is even higher than that of concentric circle MSCs at the same scan rates. To further explore the gravimetric capacitance of the prepared miniature supercapacitors, we conducted the electrochemical test of interdigital MSCs at a voltage window of 2 V and calculated the gravimetric capacitance. Figure R3.19 presents CV curves obtained under high voltage windows at different scan rates.  This part is revised as following: " Fig. 4g and Supplementary Fig.17 depicted the areal and volumetric capacitance of versatile-shaped MSCs at diverse scan rates: the interdigital MSCs always have the higher capacitance performance." The added part is inserted in Page 14, Paragraph 1, Line, 8 the detail is as following: "Considering that gravimetric capacitance is a critical factor for industrial applications, we calculated the mass loading ( Supplementary Fig. 18) and obtained the corresponding gravimetric capacitance (Supplementary Fig. 19) of MSCs with different shapes but the same size at several scan rates. The interdigital MSC exhibited the optimal gravimetric capacitance; however, the parallel strip MSC exhibited excellent gravimetric capacitance, higher than the gravimetric capacitance of the concentric circle MSC. This finding indicates that the shape design of MSCs affected performance. In interdigital MSCs, electrode material areas are used more efficiently and the contact area between the electrode material and electrolytes is greater. Furthermore, interdigital MSCs are interlaced with electrode materials that can shorten the ion diffusion pathway by narrowing the width of the fingers in the MSC and increasing the length of the interface between the active-material electrode and the electrolyte. Therefore, appropriately designing the shapes of an MSC is conducive to fast ion transfer rate, rapid charge and discharge, improved double layer storage, and enhanced rate capability 53 ." The corresponding content added in Supporting Information is as following: where e m is the effective electrode mass, t m is the total mass in the range area, e S is area of the effective electrode material, t S is the area of the normalized area, ρ is the density of the film of the electrode, h is the thickness of the film. In our work, we prepared tens of thousands of MSCs using a quantitative electrode material.
According to the mass ratio of different shapes, we can accurately calculate the mass loading of a single MSC of each shape and obtain the gravimetric capacitance.
Supplementary Figure 19: Gravimetric capacitance of three different geometries of MSCs at diverse scan rates. As shown, the interdigital MSC has the highest gravimetric capacitance of up to 290 F/g at a voltage of 0.5 V. Confounding our expectations, the parallel strip MSCs exhibited excellent gravimetric capacitance (272 F/g), which was even higher than that of the concentric circle MSCs at the same scan rates.

Reviewer's Comments
3.6. "When MSC manufacturing is focusing on the manuscript, one should check the stability of the devices with respect to cycling performances."

Our Response
We truly appreciate the reviewer for their efforts for reviewing our paper. The stability of devices is of importance in both the process and measurement of electrochemical performance. Therefore, we ensured the experimental stability and data reliability from three aspects.
(1)Stability during MSC processing As discussed earlier, we used the spatially shaped femtosecond laser to fabricate thousands of MSCs in a substantially short duration. For the process, an image loaded using a computer is used to shape the Gaussian beam emitted from the Ti:sapphire laser regenerative amplifier system, and the resulting shaped femtosecond laser directly processes GO hybrid films. Before each experiment, we calibrated the laser and evaluated its parameters to ensure that its performance was ideal. Figure R3.21 presents the interface to verify the laser state. We can only conduct experiments when all settings work normally. Subsequently, we tested the power of the laser outlet to ensure processing stability. After the laser beam was emitted from the laser source, we collected the laser in an optical path and tested its distribution uniformity. Figure   In addition, we purified air to eliminate particulate matter from the experimental area where the laser was situated and conducted daily inspection, and humidity and temperature were controlled. Figure R3.23 illustrates the environment of the experimental area and the daily temperature and humidity monitoring. In this manner, we can guarantee the repeatability of the entire process and the stability of the processing equipment.
(2) Stability of MSCs For the practical application of miniature capacitors, the cycle life is crucial.
Cycling stability with high performance remains a challenge mainly because of the easy fracture of thick electrodes during repeated charging and discharging R29 .
In the manuscript, we have described that the prepared composite film exhibits large toughness and high flexibility ( Figure 2). The structure of the 3D graphene skeleton was constructed using the femtosecond laser in one step; simultaneously, the attached manganese dioxide particles were synthesized. This 3D porous structure is highly stable and is not easily destroyed during electrode charging and discharging R30 .
Because of minimum size of the MSC, our prepared MSCs can attain a size of 10 microns, and their narrow gap can reach 500 nm; thus, transfer between ions was rapid and the transfer path was short, which reduced electrode instability in the electrolyte solution.
To demonstrate the cycle life of our MSCs, the same MSCs were sequentially subjected to 6,000 GCD cycles under different voltage windows. Figure R3.24 presents the capacitance retention of MSCs under different voltage windows. Inset: five GCD curves of interdigital MSCs before and after cycling for 6,000 times. After 6,000 cycles, the GCD curve remained almost identical to the GCD curve in the first cycle. When the voltage window was low, the capacitance retention was close to 100%, and when the voltage window was 2 V, the capacitance retention rate was above 93%. This proves that our MSCs exhibit excellent cycling stability.
To verify MSC stability, we conducted electrochemical tests over 30 days on the miniature supercapacitor fabricated. After 30 days, the miniature supercapacitor exhibited almost the same electrochemical performance as the freshly prepared MSC did. Under the same scanning rate, the CV curves of the two supercapacitors almost coincided, which indicated that the supercapacitor prepared using the shaped femtosecond laser exhibits highly stable capacitance characteristics ( Figure R3.25).  The outstanding stability can extend MSC use in numerous fields, including integrated circuits, wearable microelectronics, and medical devices.
(3) Stability of devices during electrochemical testing Electrochemical testing was performed at a CHI760E electrochemical workstation connected through a precision probe station (MPS-100S) with a microscopic system using tungsten probes (tip diameter = 5 µm) as current collectors.
To ensure a stable electrochemistry environment, the open-circuit potential (Eocp) was measured for 1 h until fluctuations were <10 mV in 10 min before every electrochemistry measurement. The electrochemical performance of MSCs was measured in a two-electrode system. In addition, our electrochemical workstation performed self-detection and troubleshooting after start-up and measured the rated resistance before and after electrochemical testing to ensure that no errors occurred.

Modifications
According to the reviewer's comments, we have revised the corresponding text in our manuscript.
The added part is inserted in Page 19, Paragraph 3, Line, 1 the detail is as following: "The electrochemical tests were carried on the MSC fabricated over 30 days and the capacitance performance is almost the same as the newly prepared MSC, which demonstrates the super stability of our MSCs (Supplementary Fig, 27)." The corresponding content added in Supporting Information is as following: To verify the stability of our MSC, we conducted electrochemical tests on the miniature supercapacitor fabricated after 30 days. We found that it exhibited almost the same electrochemical performance as the initial MSC. As shown, under the same scanning rate the CV curves of the two supercapacitors almost coincided. This also indicated that the supercapacitor prepared using a shaped femtosecond laser has highly stable capacitance characteristics.

"I can easily found that several other works with better performances for
laser irradiated graphene in the literature, however, authors didn't consider them for comparison with their data."

Our Response
We deeply appreciate the reviewer's efforts taken for reviewing our manuscript.
Thank you very much for the suggestion to compare our data with the data of studies showing the better performance of laser-irradiated graphene-based supercapacitors.  Through the aforementioned comparison, we found that the supercapacitors in some studies exhibited better performance than our supercapacitors. Most of these performance results are almost reflected in real capacitance and power density, but our energy density remains higher. For a more complete representation, we reconstructed the Ragone plot comparing the energy and power density of different laser-irradiated graphene-based supercapacitors, including some supercapacitors that exhibit more satisfactory performance than our supercapacitor in terms of one parameter ( Figure R 3.28). Furthermore, Figure R3.29 presents the area-specific Ragone plot that maps the performance of various laser-irradiated graphene-based supercapacitors. The prepared miniature supercapacitor presents obvious advantages in volume-specific energy density because of its small size, high voltage window, and small thickness. In the same manner, other supercapacitors with large thickness have exceeded in the area-specific Ragone plot. Moreover, this finding reflects that our miniaturized supercapacitor exhibits more advantages and potential in the volume level.  capacitance and ultrahigh energy density (0.23 Wh cm −3 ).

Our Response
We are very grateful for the reviewer's detailed comments, which were crucial to improving our paper.
We have carefully read the suggestions and clarified the use of the C:O ratio.  Figure R1.12 displays the XPS survey spectra for the original GO, laser-induced GO, and laser-induced GO doped with different proportions of manganese acetate (GO/Mn25%, GO/Mn50%, GO/Mn75%). Figure   R1.2-a and -b reveal that both GO and laser-induced GO display carbon and oxygen signals. After laser reduction, the O1s peak intensity of laser-induced GO is significantly reduced compared with the peak intensity of GO, indicating a loss of oxygen. Figures R1.2

Our Response
Thank you very much for your careful review of our manuscript. In our last response, we explored the classification of manganese oxides because we observed a small amount of Mn 3+ in the XPS data, which may interest other reviewers. Therefore, we supplemented relevant experiments and characterizations to explore the differences in the irradiated products of manganese ions and GO with different laser fluence.
Detailed analysis using XPS and XRD revealed that the shaped femtosecond laser can regulate the synthesis of materials and control photoinduced and photothermal-induced reduction and oxidation and manganese valence states. Altering the laser fluence can also yield heterogeneous junctions of different compositions. This is also one of the highlights of our work, which aimed to regulate the synthesis of products by using shaped lasers. We determined that more Mn2O3 was produced when the laser fluence was high. Furthermore, the optimal fluence (210 mJ/cm −2 ) also exhibited a small amount of manganese oxide or structural defects other than MnO2. Therefore, the femtosecond laser reduces GO and simultaneously facilitates the action of metal ions, which is a novel mechanism of action and provides a new approach to the synthesis of energy materials.
The coexistence of aliovalent cations (Mn 2+ , Mn 3+ , and Mn 4+ ) may facilitate the formation of more ionic defects (e.g., vacancies and misplaced ions) and electronic defects (electrons and holes), thereby altering the electronic, ionic, and catalytic properties of the manganese oxides. These defects may accelerate the kinetics of surface redox reactions. Furthermore, the mismatches induced by structural differences in different manganese oxide phases may produce additional defects (cavities, stacking faults, etc.), which facilitate the formation of porous nanoarchitectures that may enhance the transport of charged species and extend the reaction sites from the surface to the subsurface of electrodes R7 . The in situ X-ray absorption near-edge spectroscopy (XANES) spectra (Fig. R1.4a)  As illustrated in Figure R1 The corresponding contents (Fig. R1.3, Fig. R1.4 and Table R1.2) are added in Supplementary material as Supplementary Fig.17, Fig.6 and Table 3.  Fig. 1. In another word, a z-scan is needed for a 3D stereographic manufacturing unless such a manufacturing is 2D.

The individual capacitor array without proper connection is useless, as shown in many of their
figures. Note that they only measure one microcapacitor with a microprobe. This is scientific misleading to display so-called million capacitors. Will they want to use one by one? They do display two connected in serial or parallel. It is unclear how they make the connection. In summary, they do display capacitor array in a large area, but their manufacturing procedures do not support these results.

Our Response
Thank you very much for your detailed feedback regarding laser manufacturing.
Stereolithography (SLA) is an example of a line-by-line and layer-by-layer manufacturing process based on polymerization. With the development of technology, using a special phase modulator is well known for stereolithography, which facilitates the manufacturing in 2D without scanning. We did extensive literature research on the stereolithography by special phase modulator.
Stereolithography usually used DMD as a special phase modulator to fabricate 3D prototypes R10,11 , the method exposes the entire layer pattern on the surface of the liquid photopolymer. And the planar resolution of the system was found to be approximately 10 µm. The size of the three-dimensional structure processed by this method is generally between a few millimeters and a few centimeters, and the X, Y axis, especially the Z axis, needs to be moved to satisfy the three-dimensional processing. SLA is usually a rapid prototyping method for 3D polymer part fabrication. A polymer (usually highly cross-linked) is formed layer by layer through photo-induced polymerization; the light source, which is either a highly focused beam or laser, is used to initiate polymerization by photodegrading an initiator to form radicals, cations, or carbene-like species, which complicates the manufacture of other materials using SLA, especially active electrode materials.
For our technology (SSFL), the processing mechanism of our technology is different from SLA additive manufacturing by UV-light or laser-induced polymerization. The selective generation of electrode materials was realized through laser reduction and oxidation, modification, additive and subtractive manufacturing. The SSFL technique is particularly attractive because it is suitable for numerous material systems, which breaks the limitations of SLA technology for processing materials. We used the SSFL pattern on Ti3C2 MXene, MoS2, PEDOT, polymers, metals and metal organic frameworks in one step.
On the other hand, our SSFL can achieve ultra-fine structure processing, with extremely high resolution ( ＜ 500nm), and can obtain an extremely small structure with the size of 10 microns. Compared to SLA technology, we have improved the precision of micro-nano manufacturing and enabling more miniaturized manufacturing without requiring extra time for postcuring.
Furthermore, SLA uses a fixed-focus beam with an X-Y translation stage to solidify the layers, instead of galvanometric mirrors, and a rastering laser to selectively polymerize a liquid polymer resin on a layer-by-layer basis to fabricate 3D objects. The scanning microstereolithography machine processes each layer individually and requires a program to control the movement on the X, Y, and Z axis. The reviewer suggested that "a z-scan is needed for a 3D stereographic manufacturing unless the manufacturing is 2D." In our work, SSFL focuses on a number of thin film material and we used the Ti: sapphire laser regenerative amplifier system, which can generate 1,000 single pulses per second. Each shaped laser pulse can fabricate a single MSC, resulting in the fabrication of a single MSC in only 0.001 s. The translation platform need only be moved rapidly along the X-or Y-axis to perform rapid large-area machining.
The laser repetition frequency must be adjusted according to the size of the MSCs to satisfy the machining requirements under the reported experimental equipment and conditions (an X-Y stage with a maximum speed of 2,000 μm/s), otherwise the obtained MSCs overlap. When the scanning speed of the X-axis is 2,000 μm/s, the translation platform can accurately move 2,000 μm per second. A total of 20, 40, and 100 MSCs can be realized on a single path of 2,000 μm in 1 s when the size of the laser spots is 100 × 100, 50 × 50, and 20 × 20 μm 2 , respectively. The laser repetition frequency at this time is also adjusted to 20, 40, and 100 shaped laser subpulses per second. Therefore, the laser remains on at all times. We could achieve the highest machining efficiency by adjusting the repetition frequency of the laser pulse and moving the stage as quickly as possible. Therefore, we could control the stage at a speed of 2,000 μm/s and spacing of 100 μm to scan an area of 1 × 1 cm 2 along the X-Y direction to complete an area of 1 × 1 cm 2 , as the reviewer mentioned. Designing other complex procedures or shifting the spot to 100 × 100 times is unnecessary. Our SSFL method is highly operable and efficient. The actual processing speed observed exceeded 3,000 MSCs/min, which is tens or hundreds of times more efficient than previously reported processes for fabricating MSCs. Approximately 1.8 million MSCs can be fabricated in 30 min if the translation stage maintains an accuracy of <1 µm and the laser repetition frequency is adjusted to 1,000.
According to the comments of the reviewer, we have added the corresponding part in Supporting Information 1.5.
The aim of this study was to develop an method for fabricating MSCs, especially ultrathin MSCs.
Ultrathin MSCs can store energy in a very small volume and have suitable dependence and flexibility. In our previous response, we displayed a cross-section view of the processing films of different thicknesses and provided a detailed characterization (in the last response 1.1.3), which can prove the processing capacity of the SSFL in the z-axis direction, and a porous 3D composite material synthesized by SSFL.
MSCs that are tens of microns thick are relatively common among prepared ultrathin MSCs, and this is also the thickness range that can be fully processed by a laser. These MSCs do not require processing in the Z-axis direction and can be fabricated directly using a laser R5,12-14 . Figure R1.7 summarizes four studies on the direct processing of graphene-based MSCs by using lasers. These studies reported the processing of the Z-axis without scanning in the Z-axis direction and obtained 3D porous structures of graphene. The thickness of the MSCs prepared was several microns or tens of microns thick.

Our Response
Thank you very much for your time and effort in reviewing our manuscript. We designed individual light fields to prepare separate arrays of MSCs of different shapes to highlight their integrity and facilitate readers' shape perception at a glance. However, we designed corresponding light fields to prepare self-assembling and serial-parallel MSCs arrays because these independent MSCs must be combined in practical processing. We could directly obtain the array of multiple MSCs in series by controlling the spacing between the MSCs, and the multiple MSCs connected well with each other. As presented in Fig.   R1.8-a, multiple different shapes of MSCs can be obtained in series. Video 2 in the Supplementary material also illustrates the process of directly and rapidly preparing multiple MSCs in a series.
As projected, the interdigital MSCs connected in series, from a single device to six devices, which revealed the triangular charge-discharge curves and nearly rectangular shapes of EDLC behaviors. The working voltage increased from 2 to 11.39 V (Fig.   R1.8-b). To obtain an array of parallel MSCs, we connected MSCs end to end so that we only needed to improve the shape of the light field to satisfy the processing requirements. We modified the design of the pattern to produce the light field illustrated in Figure   R1.9-a. We could rapidly fabricate multiple MSCs in parallel by adjusting the spacing between individual laser spots. The MSCs fabricated using this method have suitable consistency and can be assembled arbitrarily. As illustrated in Figure R 1.9-b, the parallel MSCs arrays are obtained after laser spots processing the thin film material in order.
We could also obtain the array of serial and parallel MSCs

Our Response
Thank you very much for your detailed and invaluable feedback and for your time and effort in reviewing our manuscript. Your constructive feedback has helped us revise our manuscript, which has enabled us to improve the quality of our manuscript.
In our paper, we ignored the demonstration of series and parallel of MSCs. As reviewers have pointed out, it is difficult to connect individual MSCs in such size. But the SSFL strategy can solve this problem in our work. In order to minimize the length of the reply, the editor suggested that if there are any figures, points repeated then you may wish to place them at one instance and point the referees.
We have made detailed answers and analysis of experimental data in 1.

Our Response, which
showed the series and parallel connections of multiple MSCs clearly and performed the detailed electrochemical tests. We would be very grateful if you could refer to the above reply. Fig. 5b

Our Response
We deeply appreciate the reviewer for the suggestions for improving the quality of our paper. We are grateful to receive such excellent advice to improve our paper quality.
Electrode polarization and electrolyte decomposition occur easily in MSCs at low scan rates and high voltages. We aim to avoid this situation through the use of a favorable material design and neutral electrolyte to obtain higher Coulomb efficiency. The CV and GCD curves indicated that the symmetric MSCs possess a high working voltage of 2.0 V, which is considerably higher than the working voltage of the average MSCs. However, as mentioned by the reviewer, an asymmetrical curve was observed in our MSCs under a high voltage window (Fig. 5b). In our initial experiments, to explore the extension of the voltage window, we ignored the curve changes under the high voltage window.
We reviewed the literature to understand and analyze this behavior and improved the experimental conditions to optimize our experiment. When the MSCs were tested at much higher voltages, considerably  We determined that the CV curves of optimized MSCs at high voltages were more symmetrical than before. However, they still exhibited an upwards trend at the end, which indicated electrode polarization and electrolyte decomposition. Therefore, we performed a detailed test and calculation of Coulomb efficiency.
We calculated the Coulombic efficiency of our MSCs at different current densities under high voltage windows (2 V) using equation (1). In our initial tests, we determined that the charging and discharging times of the GCD curves were similar at different current densities. In the initial cycles, the Coulombic efficiency reached 98%. Moreover, the Coulombic efficiency was higher at a high current density as the number of cycles increased. To investigate the stability of the LIG/MnO2, the number of cycles was increased to 12,000 to observe the capacitance retention rate and Coulomb efficiency. The performance was more favorable than the original results. Figure R2.3-a displays the capacitance retention and Coulombic efficiency of the optimized MSCs. The GCD curves after 12,000 cycles are displayed in Figure R2.3-b. The GCD curves indicate high Coulomb efficiency and capacitance retention. Over 95% of the capacitance of each voltage window was retained after 12,000 cycles, and the Coulomb efficiency was close to 100%. These findings demonstrate that our MSCs have favorable electrochemical performance and can achieve a highly stable electrochemical voltage window. The corresponding contents have been modified in the manuscript.
In our manuscript, we claim that the energy density of our MSCs is similar to that of Panasonic (17500) Li-ion batteries.
We did not consider this claim carefully and fully. We measured the electrochemical cycle curves five times at different scan rates and measured the areal capacitance and volumetric capacitance of each scan. We calculated the standard error of the five values using the function. We propose an ultrafast, one-step, high-resolution, largescale SSFL method for patterning LIG/MnO2 flexible MSCs. The SSFL technique differs from previously reported methods because it can be used to directly complete the processing of electrical devices in batches without the use of any other methods or laser direct writing. Furthermore, our technology is particularly suitable for ultrathin, difficult-to-process MSCs, which have even lower volume requirements because of their small thickness. Our MSCs are only a few microns thick and can even reach a submicron thickness level. Therefore, the volume of the entire MSC can be considerably reduced, resulting in a higher volumetric capacitance and volumetric energy density.
The capacitance of LIG/MnO2 MSCs was calculated using the following equation: where I is the current applied, ϑ is the scan rate and V corresponds to the voltage range (Vf and Vi represent final voltage and the initial voltage respectively). The volumetric energy density of the LIG/MnO2 MSCs was obtained from the equation: (3) where the E , C and E  represent the energy density, capacitance of LIG/MnO2 MSC and operating voltage, respectively. An increase in the voltage window is of considerable value for increasing MSC energy density. Our MSCs extended the voltage window and achieved excellent electrochemical performance at high voltage windows. Therefore, we considered each parameter that affects energy density and designed the material system and MSC structure to obtain optimal results. Figure R 2.5 displays five sets of data to illustrate the energy density and power density of the MSCs and avoid data contingency. The five Ragone plots compare the energy density and power density of our MSCs with those of Panasonic (17500) Li-ion batteries. We determined that the highest energy density of our MSCs was close to the energy density of the Panasonic Li-ion batteries. The overall energy density of our MSCs was lower than that of Li-ion batteries. However, Panasonic Li-ion batteries achieve corresponding energy density in practical applications, and the overall performance of our MSC was not comparable. Therefore, our statement was not sufficiently rigorous. The reviewer's comment reminded us that we should maintain a rigorous attitude in scientific research and prompted us to review the comprehensive data and perform new electrochemical tests, which will be valuable for future work.

Modifications
Following the reviewer's suggestions, we have made great efforts to further present the novelty of our work in the revised manuscript, where necessary, please see page 19 line 1-2, figure 5 b and c.

Reviewer's Comments
3.1. The shape diversity study was done in the manuscript according to Fig. 18

Our Response
We truly appreciate the reviewer for the efforts for reviewing our paper. We are happy to have received the following suggestions for improving the paper quality. We have modified the corresponding text following the reviewer's comments.
We designed three electrodes with different shapes and mass loading to more comprehensively illustrate the influence of shape on capacitance. Furthermore, we redesigned MSCs of different shapes to have the same mass loading for testing their electrochemical performance, in accordance with another method (Energy Environ. Sci., 2019,12, 2507-2517).Therefore, versatile structural MSCs devices with interdigital, parallel strips and concentric circles were fabricated with specific size parameters. As illustrated in Figure  Information. The CV curves (Fig. R3.2) of all three MSC shapes were rectangular at high or low scan rates, demonstrating the high-quality capacitive performance, shape compatibility, and suitability of the MSCs processed using the SSFL method. Furthermore, the specific capacitance and the shape of the CV graph of the interdigital MSC were of high quality.

Modifications
According to the reviewer's comments, we have revised the corresponding part in our manuscript, where necessary, please see page 14 line 15-20 and Supplementary Information figure 19. figure 5

Our Response
We are very grateful to the reviewer for the suggestions and for drawing our attention to the two papers reporting that MSCs can achieve a long cycle life.
In accordance with the reviewer's comments, we verified the device performance up to 12,000 cycles.
Furthermore, to demonstrate the stable electrochemical performance of our MSCs, we calculated the corresponding Coulomb efficiency. Figure R3.3-a displays the capacitance retention and Coulombic efficiency of our MSCs, and Figure R3.3-b displays the GCD curves after 12,000 cycles, which demonstrate the high Coulomb efficiency and capacitance retention of the MSCs. Over 95% of the capacitance of each voltage window was retained after 12,000 cycles, and the Coulomb efficiency was nearly 100%. These findings demonstrate that our MSCs have satisfactory electrochemical performance and can achieve a highly stable electrochemical voltage window.

Modifications
Following the reviewer's suggestions, we have made great efforts to further present the novelty of our work in the revised manuscript, where necessary, please see figure 5 c and page 19 line 1-2. We also noticed a method for increasing the cycle life of MSCs to 100,000 cycles with a high capacitance retention (100%) R24 . The high cycle life can be attributed to the interconnected sheet-like structure of LIG and the minimal defects in its backbone, which facilitate electronic transport during GCD cycling. The unique porous structure and absence of a metal current collector in the LIG-based MSCs improved the cycling performance.

3.4.
Although the authors have addressed the comments raised by the reviewers, but the answer to the reviewer's file is too long. Several figures used multiple times, which can be avoided. The to-the-point answers will be appreciated.

Our Response
Thank you very much for the reminder. We deeply appreciate the reviewer for the suggestions for improving the quality of our paper. We have attempted to simplify the language and reduce redundancy in the figures and main text.