, Wei Lu, *,, Yousi Chen, * Wenqin Wang,

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1 Supplementary Materials for High Performance Humidity Fluctuation Sensor for Wearable Devices via Bioinspired Atomic-precise Tunable Graphene-Polymer Heterogeneous Sensing Junction Jiang He,, Peng Xiao,, Jiangwei Shi,, Yun Liang, Wei Lu, *,, Yousi Chen, * Wenqin Wang, Patrick Théato, Shiao-Wei Kuo # and Tao Chen *,, The PDF file includes: Figure S1. SEM image of the graphene oxide nanosheets. 2 Figure S2. The IDE pattern window on the PI substrate. 2 Figure S3. AFM image of the layered structure GNCP film. 3 Figure S4. Raman spectra of GNCP. 3 Figure S5. XRD patterns of GNCP with different PDA weight ration. 4 Figure S6. Long time stability of the GNCP sensor device 4 Table S1 High performance humidity sensors reported in the literature 5 Theoretical study of the hydrogen bonds interaction between PDA and water molecules 6 Figure S7. PDA molecules capture water molecules through hydrogen bonds. 7 Figure S8. Processed respiratory RH curve signal with parameters marked for the respiratory data analysis. 7 Figure S9. Raw respiratory signal under dry atmosphere and wet atmosphere. 8 Figure S10. Raw respiratory signal tested by humidity sensor in different position on the mask. 8 Figure S11. The sensor response to RH on the surface of the skin. 9 Figure S12. Images and schematic illustrations the structure of the smart wristband. 9 Figure S13. Real-time physiological and psychological monitoring subject. 10 References 10 Other Supplementary Material for this manuscript includes the following: Video 1- The RH sensor response to speaking. (AVI) Video 2- The breath monitor. (AVI) Video 3- The lie detector. (AVI) 1

2 Figure S1. SEM image of the giant graphene oxide nanosheets with a relatively wide distribution ranging from dozens of micrometers (up to ~30µm) to several micrometers (down to ~5µm) deposited on rinsed silicon wafer. Figure S2. The IDE pattern window on the PI substrate provided an outline dimension of 13 mm 30 mm, the IDE finger thickness was 20µm, and the width and gap both was 150 µm. 2

3 Figure S3. AFM image shows the thickness of layered structure GNCP-4 nano film on sensor is about 40 nm. Figure S4. (a)raman spectra of GNCP-1, GNCP -2, GNCP -3, GNCP -4, and GO. (b) I D /I G values of the above samples. Humidity-Resistance curve fitting: Dry condition (RH = 0~29%):

4 Wet condition (RH = 29~97%): log log log For calculation of RH, every dot resistance value was converted to RH value using the above calibration equations. Figure S5. Fitted Humidity-Resistance curve under dry condition (a) and wet condition (b), and their calibration equation are as above. Figure S6. (a) Long time stability of the GNCP sensor device. Current-Voltage (I-V) characteristics of the device measured after 30 and 60 days storage at constant atmosphere (RH=53%). (b) The device was bended to different angles and tested by I-V curve under 1V bias voltage. The results show no remarkable difference between the flat and bent states under different humidity condition (0%, 42% and 97%). 4

5 Table S1. Comparison of the sensing performance of our GNCP sensor with that of some previously reported ones. Measurement Sensor type Sensing material Sensitivity range Time (s) R s R r Reference Resistive Supramolecular nanofibres 10 80% RH Resistive Graphene Oxide 35 80% RH Resistive Porous Ionic Membrane % RH Resistive RGO Modified CuO 11 98% RH Resistive VS 2 ultrathin nanosheets 0 98% RH Resistive Reduced Oxide Graphene % RH Resistive Poly(dopamine)-treated graphene oxide/poly(vinyl alcohol) 30 65% RH Capacitive MoS 2 -Modified SnO % RH Capacitive Metal oxide/graphene hybrid nanocomposite 11 97% RH Capacitive Reduced graphene oxide (RGO)/poly(diallylimeth yammonium chloride) 11 97% RH % Capacitive Graphene oxide/polyelectrolyte nanocomposite film 11 97% RH

6 Resistive GNCP 0 97% RH This paper Theoretical study of the hydrogen bonds interaction between PDA and water molecules: The spontaneous formation of a bond always involves the release of some of the internal energy of the unbonded atoms and its conversion to another energy form. Clearly, the stronger the bond, and hence the greater the change in free energy ( G) that accompanies its formation, the greater is the proportion of atoms that must exist in the bonded form. This common sense idea is quantitatively expressed by the physicochemical formula. K = / K = / where G<0 is free energy, R is the universal gas constant, T is the absolute temperature, K eq is the equilibrium constant, e = 2.718, P = 1 bar and P water is pressure of water vapor. Atoms joined by chemical bonds do not remain together forever, because there also exist forces that break chemical bonds. By far the most important of these forces arises from heat energy. From the physicochemical formula, we can conclude that, as the rise of the temperature, the equilibrium shifts away from products, resulting the lose of water and increase of resistance of our sensor. The non-covalent intermolecular weak interactions, such as van der Waals interaction, hydrogen bonding, metal coordination, hydrophobic forces, electrostatic effects, π-π interaction, plays a crucial role in many biological interactions, including the interactions between proteins and DNA, and between proteins and other proteins, lie at the heart of how cells detect and respond to signals. Hydrogen bonds have energies about 10 times higher than the average energy of kinetic motion (heat) at 25 (0.6 kcal/mol). [1] Even though this force is relatively weak, it is still large enough to ensure that the right molecules (or atomic groups) interact with each other. For example, the surface of an enzyme is uniquely shaped to allow the specific attraction of its substrates. Nevertheless, because there is a significant spread in the energies of kinetic motion, many molecules with sufficient kinetic energy to break the strongest weak bonds still exist at physiological temperatures. Thus, at room temperature, weak hydrogen bonds are constantly made and broken, which ensure the interactions between the molecular in cell revisable. More importantly, the relative low free energy of week bonds ensure itself can be both made and broken apart rapidly as a result of random thermal movement. This explains why enzymes can function as fast as 10 6 times per second. [2] These features of weak interaction especially hydrogen bonding, make it great potential in the fabrication of bio-inspired sensor. 6

7 Figure S7. PDA molecules capture water molecules through hydrogen bonds. Figure S8. Processed respiratory RH curve signal with parameters marked for the respiratory data analysis. 7

8 Figure S9. Raw respiratory signal under dry atmosphere (RH 35%, T 25 ) (a) and wet atmosphere (RH 75%, T 25 ). Figure S10. Raw respiratory signal of the prepared sensing devices, in which the humidity sensor is placed at different positions of the breath receiving masks. 8

9 Figure S11. (a) The schematics of RH distribution on the near surface of a fingertip. (b) Current-Finger distance diagram on the near surface of a fingertip measured by the as-established humidity sensor. Figure S12. (a) A subject wearing the smart wristband and two electrode patches for skin RH and skin resistance signal simultaneously detecting. (b) Photograph of the smart wristband. (c) The structure of the smart wristband. (d) The photo of breathable superhydrophobic fabric. This material can prevent the liquid perspiration and skin unintentionally contacting onto the sensor surface. 9

10 Figure S13. (a) A subject wearing a smart wristband and real-time humidity monitoring results (right) using the sensor. The sensor accurately measured skin humidity of % during mild exercise. (b) Photograph (left) of a subject wearing a smart head patch and real-time humidity monitoring results during math exercise in limited time (nervous state) and music enjoyment (relax state) using the sensor. References and Notes 1. Watson, J. D.; Baker, T.; Bell, S.; Gann, A.; Levine, M.; Losick, R., Molecular biology of the gene. Pearson/Benjamin Cummings: 2003; p Lodish, H., Molecular cell biology. Macmillan: 2008, p Mogera, U.; Sagade, A. A.; George, S. J.; Kulkarni, G. U., Ultrafast Response Humidity Sensor Using Supramolecular Nanofibre and Its Application in Monitoring Breath Humidity And Flow. Sci. Rep. 2014, 4, Borini, S.; White, R.; Wei, D.; Astley, M.; Haque, S.; Spigone, E.; Harris, N.; Kivioja, J.; Ryhänen, T., Ultrafast Graphene Oxide Humidity Sensors. ACS Nano 2013, 7, Li, T.; Li, L.; Sun, H.; Xu, Y.; Wang, X.; Luo, H.; Liu, Z.; Zhang, T., Porous Ionic Membrane Based Flexible Humidity Sensor and its Multifunctional Applications. Adv. Sci, 2017, 4, Wang, Z.; Xiao, Y.; Cui, X.; Cheng, P.; Wang, B.; Gao, Y.; Li, X.; Yang, T.; Zhang, T.; Lu, G., Humidity-Sensing Properties of Urchinlike CuO Nanostructures Modified by Reduced Graphene Oxide. ACS Appl.Mater. Interfaces 2014, 6, Feng, J.; Peng, L.; Wu, C.; Sun, X.; Hu, S.; Lin, C.; Dai, J.; Yang, J.; Xie, Y., Giant Moisture Responsiveness of VS2 Ultrathin Nanosheets for Novel Touchless Positioning Interface. Adv. Mater. 2012, 24,

11 8. Wang, X.; Xiong, Z.; Liu, Z.; Zhang, T., Exfoliation at the Liquid/Air Interface to Assemble Reduced Graphene Oxide Ultrathin Films for a Flexible Noncontact Sensing Device. Adv. Mater. 2015, 27, Hwang, S.-H.; Kang, D.; Ruoff, R. S.; Shin, H. S.; Park, Y.-B., Poly(vinyl alcohol) Reinforced and Toughened with Poly(dopamine)-Treated Graphene Oxide, and Its Use for Humidity Sensing. ACS Nano 2014, 8, Zhang, D.; Sun, Y. e.; Li, P.; Zhang, Y., Facile Fabrication of MoS2-Modified SnO2 Hybrid Nanocomposite for Ultrasensitive Humidity Sensing. ACS Appl. Mater. Interfaces 2016, 8, Zhang, D.; Chang, H.; Li, P.; Liu, R.; Xue, Q., Fabrication and Characterization of an Ultrasensitive Humidity Sensor based on Metal Oxide/Graphene Hybrid Nanocomposite. Sensor. Actuat. B-Chem. 2016, 225, Zhang, D.; Tong, J.; Xia, B., Humidity-Sensing Properties of Chemically Reduced Graphene Oxide/Polymer Nanocomposite Film Sensor Based on Layer-By-Layer Nano Self-Assembly. Sensor. Actuat. B-Chem. 2014, 197, Zhang, D.; Tong, J.; Xia, B.; Xue, Q., Ultrahigh Performance Humidity Sensor Based on Layer-By-Layer Self-Assembly of Graphene Oxide/Polyelectrolyte Nanocomposite Film. Sensor. Actuat. B-Chem. 2014, 203,