Highly Thermally Conductive and Structurally Ultra‑Stable Graphitic Films with Seamless Heterointerfaces for Extreme Thermal Management

Highly thermally conductive graphitic film(GF)materials have become a competitive solution for the thermal management of high-power electronic devices.However,their catastrophic structural failure under extreme alternating thermal/cold shock poses a significant challenge to reliability and safety.Here,we present the first investigation into the structural failure mechanism of GF during cyclic liquid nitrogen shocks(LNS),which reveals a bubbling process characterized by“permeation-diffusion-deformation”phenomenon.To overcome this long-standing structural weakness,a novel metal-nanoarmor strategy is proposed to construct a Cu-modified graphitic film(GF@Cu)with seamless heterointerface.This well-designed interface ensures superior structural stability for GF@Cu after hundreds of LNS cycles from 77 to 300 K.Moreover,GF@Cu maintains high thermal conductivity up to 1088 W m^(−1)K^(−1)with degradation of less than 5%even after 150 LNS cycles,superior to that of pure GF(50%degradation).Our work not only offers an opportunity to improve the robustness of graphitic films by the rational structural design but also facilitates the applications of thermally conductive carbon-based materials for future extreme thermal management in complex aerospace electronics.

Local thermal conductivity of inhomogeneous nano-fluidic films:A density functional theory perspective

Combining the mean field Pozhar-Gubbins(PG)theory and the weighted density approximation,a novel method for local thermal conductivity of inhomogeneous fluids is proposed.The correlation effect that is beyond the mean field treatment is taken into account by the simulation-based empirical correlations.The application of this method to confined argon in slit pore shows that its prediction agrees well with the simulation results,and that it performs better than the original PG theory as well as the local averaged density model(LADM).In its further application to the nano-fluidic films,the influences of fluid parameters and pore parameters on the thermal conductivity are calculated and investigated.It is found that both the local thermal conductivity and the overall thermal conductivity can be significantly modulated by these parameters.Specifically,in the supercritical states,the thermal conductivity of the confined fluid shows positive correlation to the bulk density as well as the temperature.However,when the bulk density is small,the thermal conductivity exhibits a decrease-increase transition as the temperature is increased.This is also the case in which the temperature is low.In fact,the decrease-increase transition in both the small-bulk-density and low-temperature cases arises from the capillary condensation in the pore.Furthermore,smaller pore width and/or stronger adsorption potential can raise the critical temperature for condensation,and then are beneficial to the enhancement of the thermal conductivity.These modulation behaviors of the local thermal conductivity lead immediately to the significant difference of the overall thermal conductivity in different phase regions.

Molecular simulation and experimental investigation of thermal conductivity of flexible graphite film

Flexible graphite film(FGF),as a traditional interface heat dissipation material,has high anisotropy.It is a challenge to enhance both in-plane and through-plane thermal conductivity of FGF.For this reason,the effects of oxygen content,layer spacing,density and particle size on the in-plane and through-plane thermal conductivity of FGF were studied by both molecular simulation and experimental investigation.The simulation results indicate that the ways to improve the thermal conductivity of FGF include reducing oxygen content and layer spacing,increasing the density and matching the size of graphite sheets.The FGF prepared from room temperature exfoliated graphite(RTFGF)has a wide range of adjustable density(1.3–2.0 g/cm^(3))and thickness(50–400μm).The thermal conductivity of the RTFGF is significantly improved after heat treatment owing to reduced oxygen content and layer spacing,which is consistent with the simulation results.Moreover,RTFGF with both high in-plane(518 W·m^(-1)·K^(-1))and through-plane(7.2 W·m^(-1)·K^(-1))thermal conductivity can be obtained by particle size matching of graphite.

Emerging Flexible Thermally Conductive Films:Mechanism,Fabrication,Application

Effective thermal management is quite urgent for electronics owing to their ever-growing integration degree,operation frequency and power density,and the main strategy of thermal management is to remove excess energy from electronics to outside by thermal conductive materials.Compared to the conventional thermal management materials,flexible thermally conductive films with high in-plane thermal conductivity,as emerging candidates,have aroused greater interest in the last decade,which show great potential in thermal management applications of next-generation devices.However,a comprehensive review of flexible thermally conductive films is rarely reported.Thus,we review recent advances of both intrinsic polymer films and polymer-based composite films with ultrahigh in-plane thermal conductivity,with deep understandings of heat transfer mechanism,processing methods to enhance thermal conductivity,optimization strategies to reduce interface thermal resistance and their potential applications.Lastly,challenges and opportunities for the future development of flexible thermally conductive films are also discussed.

Temperature-mediated structural evolution of vapor–phase deposited cyclosiloxane polymer thin films for enhanced mechanical properties and thermal conductivity

Polymer-derived ceramic(PDC) thin films are promising wear-resistant coatings for protecting metals and carbon-carbon composites from corrosion and oxidation.However,the high pyrolysis temperature hinders the applications on substrate materials with low melting points.We report a new synthesis route for PDC coatings using initiated chemical vapor deposited poly(1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane)(pV_3D_3) as the precurs or.We investigated the changes in siloxane moieties and the network topology,and proposed a three-stage mechanism for the thermal annealing process.The rise of the connectivity number for the structures obtained at increased annealing temperatures was found with strong correlation to the enhanced mechanical properties and thermal conductivity.Our PDC films obtained via annealing at 850℃ exhibit at least 14.6% higher hardness than prior reports for PDCs synthesized below 1100℃.Furthermore,thermal conductivity up to 1.02 W(mK)^(-1) was achieved at the annealing temperature as low as 700℃,which is on the same order of magnitude as PDCs obtained above 1100℃.Using minimum thermal conductivity models,we found that the thermal transport is dominated by diffusons in the films below the percolation of rigidity,while ultra-short mean-free path phonons contribute to the thermal conductivity of the films above the percolation threshold.The findings of this work provide new insights for the development of wear-resistant and thermally conductive PDC thin films for durable protection coatings.

Conductive Polyaniline/Cellulose/Graphite Composite Films with High Thermal Stability and Antibacterial Activity

Functional composite films were successfully prepared from cellulose, graphite(GP), and polyaniline(PANI) using a combination of physical and chemical processes. Cellulosewasdissolved in N-methylmorpholine-N-oxide monohydrate(NMMO) and regenerated in water to form the matrix. GP was dispersed in the NMMO solvent prior to the dissolution of the cellulose, and PANI was deposited on the surfaces of the cellulose/GP films by in situ chemical polymerization. The structures of the PANI/cellusose/GP composite films were investigated using X-ray diffraction analysis, Fourier transform infrared spectroscopy, scanning electron microscopy(SEM), and SEM/energy-dispersive X-ray spectroscopy. The mechanical strengths, thermal stabilities, conductivities, and antibacterial activities of the films were studied in detail. The results showed that GP formed a multilayered structure in the cellulose matrix and that the PANI nanoparticles were tightly wrapped on the film surface. The film thickness increased from 40 mm to 100 mm after the addition of GP and PANI. The tensile strength of the composite films was 80~107 MPa, with the elongation at break being 3%~10%. The final residual weight of the composite films was as high as 65%, and the conductivity of the composite films reached 14.36 S/m. The cellulose matrix ensured that the films were flexible and exhibited desirable mechanical properties, while the GP filler significantly improved the thermal stability of the films. The PANI coating acted as a protective layer during burning and provided good electrical conductivity and antibacterial activity against Escherichia coli; both of these characteristics were slightly enhanced by the incorporation of GP. These PANI/cellulose/GP composite films should be suitable for use in electronics, antistatic packing, and numerous other applications.

Hierarchically Multifunctional Polyimide Composite Films with Strongly Enhanced Thermal Conductivity

The development of lightweight and integration for electronics requires flexible films with high thermal conductivity and electromagnetic interference(EMI) shielding to overcome heat accumulation and electromagnetic radiation pollution.Herein,the hierarchical design and assembly strategy was adopted to fabricate hierarchically multifunctional polyimide composite films,with graphene oxide/expanded graphite(GO/EG) as the top thermally conductive and EMI shielding layer,Fe_(3)O_(4)/polyimide(Fe_(3)O_(4)/PI) as the middle EMI shielding enhancement layer and electrospun PI fibers as the substrate layer for mechanical improvement.PI composite films with 61.0 wt% of GO/EG and 23.8 wt% of Fe_(3)O_(4)/PI exhibits high in-plane thermal conductivity coefficient(95.40 W(m K)^(-1)),excellent EMI shielding effectiveness(34.0 dB),good tensile strength(93.6 MPa) and fast electric-heating response(5 s).The test in the central processing unit verifies PI composite films present broad application prospects in electronics fields.

Printable Aligned Single-Walled Carbon Nanotube Film with Outstanding Thermal Conductivity and Electromagnetic Interference Shielding Performance

Ultrathin,lightweight,and flexible aligned single-walled carbon nanotube(SWCNT)films are fabricated by a facile,environmentally friendly,and scalable printing methodology.The aligned pattern and outstanding intrinsic properties render“metal-like”thermal conductivity of the SWCNT films,as well as excellent mechanical strength,flexibility,and hydrophobicity.Further,the aligned cellular microstructure promotes the electromagnetic interference(EMI)shielding ability of the SWCNTs,leading to excellent shielding effectiveness(SE)of~39 to 90 dB despite a density of only~0.6 g cm^(−3) at thicknesses of merely 1.5-24μm,respectively.An ultrahigh thickness-specific SE of 25693 dB mm^(−1) and an unprecedented normalized specific SE of 428222 dB cm^(2)g^(−1) are accomplished by the freestanding SWCNT films,significantly surpassing previously reported shielding materials.In addition to an EMI SE greater than 54 dB in an ultra-broadband frequency range of around 400 GHz,the films demonstrate excellent EMI shielding stability and reliability when subjected to mechanical deformation,chemical(acid/alkali/organic solvent)corrosion,and high-/low-temperature environments.The novel printed SWCNT films offer significant potential for practical applications in the aerospace,defense,precision components,and smart wearable electronics industries.

Enhancing the thermal conductivity of polymer-assisted deposited Al_2O_3 film by nitrogen doping

Polymer-assisted deposition technique has been used to deposit Al2O3 and N-doped Al2O3 （AION） thin films on Si（100） substrates. The chemical compositions, crystallinity, and thermal conductivity of the as-grown films have been characterized by X-ray photoelectron spectroscopy （XPS）, X-ray diffraction （XRD）, and 3-omega method, respectively. Amorphous and polycrystalline Al2O3 and AlON thin films have been formed at 700 ℃ and 1000 ℃. The thermal conductivity results indicated that the effect of nitrogen doping on the thermal conductivity is determined by the competition of the increase of Al-N bonding and the suppression of crystallinity. A 67% enhancement in thermal conductivity has been achieved for the samples grown at 700 ℃, demonstrating that the nitrogen doping is an effective way to improve the thermal performance of polymer-assisted-deposited Al2O3 thin films at a relatively low growth temperature.

Effects of deposition parameters on microstructure and thermal conductivity of diamond films deposited by DC arc plasma jet chemical vapor deposition

The uniform diamond films with 60 mm in diameter were deposited by improved DC arc plasma jet chemical vapor deposition technique. The structure of the film was characterized by scanning electronic microcopy(SEM) and laser Raman spectrometry. The thermal conductivity was measured by a photo thermal deflection technique. The effects of main deposition parameters on microstructure and thermal conductivity of the films were investigated. The results show that high thermal conductivity, 10.0 W/(K·cm), can be obtained at a CH4 concentration of 1.5% (volume fraction) and the substrate temperatures of 880-920 ℃ due to the high density and high purity of the film. A low pressure difference between nozzle and vacuum chamber is also beneficial to the high thermal conductivity.

Influences of vacancy defects on thermal conductivities of Ge thin films

The effects of vacancy defects on the thermal conductivity of Ge thin films were investigated by employing molecular dynamics （MD） simula- tions and theoretical analysis based on the Boltzmann equation. Both the MD and theoretical results show that the lattice thermal conductivity dramatically decreases with the increasing of vacancy concentration at 400 and 500 K. In addition, the dependence of vacancy concentration on the thermal conductivity of Ge thin films becomes less sensitive as the temperature increases. Theoretical results also confirm that the major part of the lattice thermal conductivity reduction is associated with the point-defect scattering and phonon-phonon scattering processes.

Dependence of Thermal Annealing on Transparent Conducting Properties of HoF_3-Doped ZnO Thin Films

A kind of n-type HoF_3-doped zinc oxide-based transparent conductive film has been developed by electron beam evaporation and studied under thermal annealing in air and vacuum at temperatures 100–500℃.Effective substitutional dopings of F to O and Ho to Zn are realized for the films with smooth surface morphology and average grain size of about 50 nm.The hall mobility,electron concentration,resistivity and work function for the asdeposited films are 47.89 cm^2/Vs,1.39×10^(20)cm^(-3),9.37×10^(-4)Ω·cm and 5.069 eV,respectively.In addition,the average transmittance in the visible region(400–700 nm)approximates to 87%.The HoF_3:ZnO films annealed in air and vacuum can retain good optoelectronic properties under 300℃,thereinto,more stable electrical properties can be found in the air-annealed films than in the vacuum-annealed films,which is assumed to be a result of improved nano-crystalline lattice quality.The optimized films for most parameters can be obtained at 200℃ for the air-annealing case and at room temperature for the vacuum annealing case.The advisable optoelectronic properties imply that HoF_3:ZnO can facilitate carrier injection and has promising applications in energy and light sources as transparent electrodes.

Accurate determination of anisotropic thermal conductivity for ultrathin composite film

Highly anisotropic thermal conductive materials are of significance in thermal management applications. However,accurate determination of ultrathin composite thermal properties is a daunting task due to the tiny thermal conductance,severely hindering the further exploration of novel efficient thermal management materials, especially for size-confined environments. In this work, by utilizing a hybrid measuring method, we demonstrate an accurate determination of thermal properties for montmorillonite/reduced graphene oxide(MMT/r GO) composite film with a thickness range from 0.2 μm to2 μm. The in-plane thermal conductivity measurement is realized by one-dimensional(1D) steady-state heat conduction approach while the cross-plane one is achieved via a modified 3ω method. As-measured thermal conductivity results are cross-checked with different methods and known materials, revealing the high measurement accuracy. A high anisotropic ratio of 60.5, independent of composite thickness, is observed in our measurements, further ensuring the negligible measurement error. Notably, our work develops an effective approach to the determination of ultrathin composite thermal conductivity, which may promote the development of ultrathin composites for potential thermal-related applications.

Studies on Thermal Conductivity of Diamond Film

Diamond films were prepared by electron-assisted chemical vapor deposition (EACVD) system, and the thermal diffusivities of the films with or without substrate were studied by use of photothermal deflection (PTD) technique. The results show that less non-diamond component and larger crystalline size result in higher thermal conductivity of CVD diamond film. The influence of substrate on the measurement of thermal conductivity of the film was investigated, and a simple two-layer heat conduction model is given to account for the influence and used to draw the thermal conductivity of the film from the effective thermal diffusivity of film/substrate system.

Thermally conductive polyvinyl alcohol composite films via introducing hetero-structured MXene@silver fillers

Ag nanoparticles were in-situ grown on the surface of MXene nanosheets to prepare thermally conductive hetero-structured MXene@Ag fillers.With polyvinyl alcohol(PVA)as the polymer matrix,thermally conductive MXene@Ag/PVA composite films were fabricated by the processes of solution blending,pouring,evaporative self-assembly.With the same mass fraction,MXene@Ag-III(MXene/Ag,2:1,w/w)presents more significant improvement in thermal conductivity coefficient(λ)than MXene@Ag,single MXene,Ag,simply blending MXene/Ag.MXene@Ag-III/PVA composite films show dual functions of excellent thermal conductivity and electromagnetic interference(EMI)shielding.When the mass fraction of MXene@Ag-III is 60 wt.%,the in-planeλ(λ_(∥)),through-planeλ(λ_(⊥)),EMI shielding effectiveness(EMI SE)are 3.72 and 0.41 W/(m∙K),32 dB,which are increased by 3.1,1.3,105.7 times than those of pure PVA film(0.91 and 0.18 W/(m∙K),0.3 dB),respectively.The 60 wt.%MXene@Ag-III/PVA composite film also has satisfying mechanical and thermal properties,with Young’s modulus,glass transition temperature,heat resistance index of 3.8 GPa,58.5 and 175.3℃,respectively.

Thermally Conductive Polyimide/Boron Nitride Composite Films with Improved Interfacial Compatibility Based on Modified Fillers by Polyimide Brushes

Polyimide-based composite films with high thermal conductivity,good mechanical property and electrical insulating performance are urgently needed in the electronics and microelectronics fields.As one of the key technical challenges to be solved,interfacial compatibility between filler and matrix plays an important role for composite film.Herein,boron nitride was modified by grafting polyimide brushes via a twostep method,and a series of thermally conductive polyimide/boron nitride composite films were prepared.Both characterization and performance results proved that the interfacial interaction and compatibility was greatly enhanced,resulting in a significant reduction in defects and interfacial thermal resistance.The interphase width of transition zone between two phases was also efficiently enlarged due to polyimide brushes grafted on filler surface.As a result,composite films based on polyimide-grafted boron nitride exhibited significantly improved properties compared with those based on pristine filler.Tensile strength can reach up to 80 MPa even if the filler content is as high as 50 wt%.The out-of-plane and in-plane thermal conductivity of composite film increased to 0.841 and 0.850 W·m^(-1)·K^(-1),respectively.In addition,thermal and dielectric properties of composite films were also enhanced to some extent.The above results indicate that surface modification by chemically grafting polymer brushes is an effective method to improve two-phase interfacial compatibility so as to prepare composite film with enhanced properties.

An Improved Thermal Conductivity Measurement Scheme for Macroscopic Graphitic Films Using the Laser Flash Method

Achieving efficient thermal management urges to exploit high-thermal-conductivity materials to satisfy the boosted demand of heat dissipation.It is critical to adopt standardized characterization protocols to evaluate the intrinsic thermal conductivity of thermal management materials.However,for the most representative laser flash method,the lack of standard measurement methodology and systematic description on the thermal diffusivity and influencing factors has led to significant deviations and confusion of the thermal conduction performance in the emerging thermal management application.Here,the measurement error factors of thermal diffusivity by the common laser flash analyzer(LFA)are discussed.Taking high-thermal-conductivity graphitic film(GF)as a typical case,the key factors are analyzed to guide the measurement protocol of related carbon-based thermal management materials.The basic principle of the LFA measurement,actual pre-processing conditions,instrument parameters setting,and data analysis are elaborated for accurate measurements.Furthermore,the graphene thick films and common isotropic materials are also extended to meet various thermal measurement requirements.Based on the existing practical problems,we propose a feasible test flow to achieve a unified and standardized thermal conductivity measurement,which is beneficial to the rapid development of carbon-based thermal management materials.

Graphene film for thermal management:A review

Thermal conductivity and thermal dissipation are of great importance for modern electronics due to the increased transistor density and operation frequency of contemporary integrated circuits.Due to its exceptionally high thermal conductivity,graphene has drawn considerable interests worldwide for heat spreading and dissipation.However,maintaining high thermal conductivity in graphene laminates(the basic technological unit)is a significant technological challenge.Aiming at highly thermal conductive graphene films(GFs),this prospective review outlines the most recent progress in the production of GFs originated from graphene oxide due to its great convenience in film processing.Additionally,we also consider such issues as film assembly,defect repair and mechanical compression during the post-treatment.We also discuss the thermal conductivity in in-plane and through-plane direction and mechanical properties of GFs.Further,the current typical applications of GFs are presented in thermal management.Finally,perspectives are given for future work on GFs for thermal management.

A 3D graphene/polyimide fiber framework with improved thermal conductivity and mechanical performance

The integration of electronic components and the popularity of flexible devices have come up with higher expectations for the heat dissipation capability and comprehensive mechanical performance of thermal management materials.In this work,after the modification of polyimide(PI)fibers through oxidation and amination,the obtained PDA@OPI fibers(polydopamine(PDA)-modified pre-oxidized PI fibers)with abundant amino groups were mixed into graphene oxide(GO)to form uniform GO-PDA@OPI composites.Followed by evaporation,carbonization,graphitization and mechanical compaction,the G-gPDA@OPI films with a stable three-dimensional(3D)long-range interconnected covalent structure were built.In particular,due to the rich covalent bonds between GO layers and PDI@OPI fibers,the enhanced synergistic graphitization promotes an ordered graphitized structure with less interlayer distance between adjacent graphene sheets in composite film.As a result,the optimized G-gPDA@OPI film displays an improved tensile strength of 78.5 MPa,tensile strain of 19.4%and thermal conductivity of 1028 W/(m·K).Simultaneously,it also shows superior flexibility and high resilience.This work provides an easily-controlled and relatively low-cost route for fabricating multifunctional graphene heat dissipation films.

Heat transfer characteristics of thin power-law liquid films over horizontal stretching sheet with internal heating and variable thermal coefficient

The effect of internal heating source on the film momentum and thermal transport characteristic of thin finite power-law liquids over an accelerating unsteady horizontal stretched interface is studied. Unlike most classical works in this field, a general surface temperature distribution of the liquid film and the generalized Fourier＇s law for varying thermal conductivity are taken into consideration. Appropriate similarity transformations are used to convert the strongly nonlinear governing partial differential equations （PDEs） into a boundary value problem with a group of two-point ordinary differential equations （ODEs）. The correspondence between the liquid film thickness and the unsteadiness parameter is derived with the BVP4C program in MATLAB. Numerical solutions to the self-similarity ODEs are obtained using the shooting technique combined with a Runge-Kutta iteration program and Newton＇s scheme. The effects of the involved physical parameters on the fluid＇s horizontal velocity and temperature distribution are presented and discussed.