Strongly reduced thermal conductivity in hybrid ZnO/nanocellulose thin films


Utilizing a combination of atomic layer deposition and dip-coating techniques, we have incorporated natural nanocellulose fibers into an inorganic matrix in order to create a layered hybrid inorganic–organic thin-film structure. Such layer-engineered hybrid materials with an unorthodox combination of components are highly potential candidates for exciting new properties. Here, we show a more than an order of magnitude reduction in the cross-plane thermal conductivity for ZnO thin films achieved with the regular inclusion of the cellulose nanofiber layers. We foresee that a similar approach as presented here for ZnO could also be applied to other inorganic materials based on earth-abundant elements to influence their thermal transport properties.

This is a preview of subscription content, log in to check access.

Figure 1
Figure 2
Figure 3


  1. 1

    Klemm D, Kramer F, Moritz S, Lindström T, Ankerfors M, Gray D, Dorris A (2011) Nanocelluloses: a new family of nature-based materials. Angew Chem Int Ed 50:5438–5466

    Article  Google Scholar 

  2. 2

    Isogai A, Saito T, Fukuzumi H (2011) TEMPO-oxidized cellulose nanofibers. Nanoscale 3:71–85

    Article  Google Scholar 

  3. 3

    Lee K-Y, Aitomäki Y, Berglund LA, Oksman K, Bismarck A (2014) On the use of nanocellulose as reinforcement in polymer matrix composites. Compos Sci Technol 105:15–27

    Article  Google Scholar 

  4. 4

    McKee JR, Appel EA, Seitsonen J, Kontturi E, Scherman OA, Ikkala O (2014) Healable, stable and stiff hydrogels: combining conflicting properties using dynamic and selective three-component recognition with reinforcing cellulose nanorods. Adv Funct Mater 24:2706–2713

    Article  Google Scholar 

  5. 5

    Hakalahti M, Mautner A, Johansson L-S, Hänninen T, Setälä H, Kontturi E, Bismarck A, Tammelin T (2016) Direct interfacial modification of nanocellulose films for thermoresponsive membrane templates. ACS Appl Mater Interfaces 8:2923–2927

    Article  Google Scholar 

  6. 6

    Ye C, Malak ST, Hu K, Wu W, Tsukruk VV (2015) Cellulose nanocrystal microcapsules as tunable cages for nano- and microparticles. ACS Nano 9:10887–10895

    Article  Google Scholar 

  7. 7

    Schyrr B, Pasche S, Voirin G, Weder C, Simon YC, Foster EJ (2014) Biosensors based on porous cellulose nanocrystal-poly(vinyl alcohol) scaffolds. ACS Appl Mater Interfaces 6:12674–12683

    Article  Google Scholar 

  8. 8

    Wang J, Cheng Q, Jiang L (2014) Synergistic toughening of bioinspired poly(vinyl alcohol)-clay-nanofibrillar cellulose artificial nacre. ACS Nano 8:2739–2745

    Article  Google Scholar 

  9. 9

    Olsson RT, Azizi Samir MAS, Salazar-Alvarez G, Belova L, Ström V, Berglund LA, Ikkala O, Nogues J, Gedde UW (2010) Making flexible magnetic aerogels and stiff magnetic nanopaper using cellulose nanofibrils as templates. Nature Nanotechnol 5:584–588

    Article  Google Scholar 

  10. 10

    Chen M, Kang H, Gong Y, Guo J, Zhang H, Liu R (2015) Bacterial cellulose supported gold nanoparticles with excellent catalytic properties. ACS Appl Mater Interfaces 7:21717–21726

    Article  Google Scholar 

  11. 11

    Chen G (1998) Thermal conductivity and ballistic-phonon transport in the cross-plane direction of superlattices. Phys Rev B 57(23):14958–14973

    Article  Google Scholar 

  12. 12

    Giri A, Niemelä J-P, Tynell T, Gaskins JT, Donovan BF, Karppinen M, Hopkins PE (2016) Heat-transport mechanisms in molecular building blocks of inorganic/organic hybrid superlattices. Phys Rev B 93:115310

    Article  Google Scholar 

  13. 13

    Giri A, Niemelä J-P, Szwejkowski CJ, Karppinen M, Hopkins PE (2016) Reduction in thermal conductivity and tunable heat capacity of inorganic/organic hybrid superlattices. Phys Rev B 93:024201

    Article  Google Scholar 

  14. 14

    Niemelä J-P, Giri A, Hopkins PE, Karppinen M (2015) Ultra-low thermal conductivity in TiO2: C superlattices. J Mater Chem A 3:11527–11532

    Article  Google Scholar 

  15. 15

    Hänninen T, Orelma H, Laine J (2015) TEMPO oxidized cellulose thin films analysed by QCM-D and AFM. Cellulose 22:165–171

    Article  Google Scholar 

  16. 16

    Qi Z-D, Saito T, Fan Y, Isogai A (2012) Multifunctional coating films by layer-by-layer deposition of cellulose and chitin nanofibrils. Biomacromolecules 13:553–558

    Article  Google Scholar 

  17. 17

    Yoon B, Lee BH, George SM (2012) Highly conductive and transparent hybrid organic–inorganic zincone thin films using atomic and molecular layer deposition. J Phys Chem C 116:24784–24791

    Article  Google Scholar 

  18. 18

    Tynell T, Terasaki I, Yamauchi H, Karppinen M (2013) Thermoelectric characteristics of (Zn, Al)O/hydroquinone superlattices. J Mater Chem A 1:13619–13624

    Article  Google Scholar 

  19. 19

    Tynell T, Giri A, Gaskins J, Hopkins PE, Mele P, Miyazaki K, Karppinen M (2014) Efficiently suppressed thermal conductivity in ZnO thin films via periodic introduction of organic layers. J Mater Chem A 2:12150–12152

    Article  Google Scholar 

  20. 20

    Wan C, Gu X, Dang F, Itoh T, Wang Y, Sasaki H, Kondo M, Koga K, Yabuki K, Snyder GJ, Yang R, Koumoto K (2015) Flexible n-type thermoelectric materials by organic intercalation of layered transition metal dichalcogenide TiS2. Nat Mater 14:622–627

    Article  Google Scholar 

  21. 21

    Karttunen AJ, Tynell T, Karppinen M (2016) Layer-by-layer design of nanostructured thermoelectrics: first-principles study of ZnO: organic superlattices fabricated by ALD/MLD. Nano Energy 22:338–348

    Article  Google Scholar 

  22. 22

    Snyder GJ, Toberer ES (2008) Complex thermoelectric materials. Nat Mater 7:105–114

    Article  Google Scholar 

  23. 23

    George SM (2010) Atomic layer deposition: an overview. Chem Rev 110:111–131

    Article  Google Scholar 

  24. 24

    George SM, Yoon B, Dameron AA (2009) Surface chemistry for molecular layer deposition of organic and hybrid organic–inorganic polymers. Acc Chem Res 42(4):498–508

    Article  Google Scholar 

  25. 25

    Sundberg P, Karppinen M (2014) Organic and inorganic–organic thin film structures by molecular layer deposition: A review. Beilstein J Nanotechnol 5:1104–1136

    Article  Google Scholar 

  26. 26

    Gregorczyk K, Knez M (2016) Hybrid nanomaterials through molecular and atomic layer deposition: top down, bottom up, and in-between approaches to new materials. Prog Mater Sci 75:1–37

    Article  Google Scholar 

  27. 27

    Tynell T, Yamauchi H, Karppinen M (2014) Hybrid inorganic–organic superlattice structures with atomic layer deposition/molecular layer deposition. J Vac Sci Technol A 32(1):01A105

    Article  Google Scholar 

  28. 28

    Degen A, Kosec M (2000) Effect of pH and impurities on the surface charge of zinc oxide in aqueous solution. J Eur Ceram Soc 20:667–673

    Article  Google Scholar 

  29. 29

    Alvarez-Quintana J, Martínez E, Pérez-Tijerina E, Pérez-Garcia SA, Rodríguez-Viejo J (2010) Temperature dependent thermal conductivity of polycrystalline ZnO films. J Appl Phys 107:063713

    Article  Google Scholar 

Download references


The present work has received funding from the European Research Council under the European Union’s Seventh Framework Programme (FP/2007-2013)/ERC Advanced Grant Agreement (No. 339478) and ERC Proof-of-Concept Grant Agreement (No. 712738), Academy of Finland (Nos. 259500, 292431, 303452), the Aalto School of Chemical Technology—VTT Forest Meets Chemistry Programme and from the United States Army Research Office (No. W911NF-16-1-0320).

Author information



Corresponding author

Correspondence to Maarit Karppinen.

Ethics declarations

Conflicts of interest

The authors declare that they have no conflict of interest.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 32 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Jin, H., Marin, G., Giri, A. et al. Strongly reduced thermal conductivity in hybrid ZnO/nanocellulose thin films. J Mater Sci 52, 6093–6099 (2017).

Download citation


  • Atomic Layer Deposition
  • Hybrid Film
  • Layered Hybrid
  • Cellulose Nanofibers
  • Hybrid Thin Film