Ultrafast Laser-Induced Excellent Thermoelectric Performance of PEDOT:PSS Films

Because poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate)(PEDOT:PSS)is water processable,thermally stable,and highly conductive,PEDOT:PSS and its composites have been considered to be one of the most promising flexible thermoelectric materials.However,the PEDOT:PSS film prepared from its commercial aqueous dispersion usually has very low conductivity,thus cannot be directly utilized for TE applications.Here,a simple environmental friendly strategy via femtosecond laser irradiation without any chemical dopants and treatments was demonstrated.Under optimal conditions,the electrical conductivity of the treated film is increased to 803.1 S cm^(-1)from 1.2 S cm^(-1)around three order of magnitude higher,and the power factor is improved to 19.0μW m^(-1)K^(-2),which is enhanced more than 200 times.The mechanism for such remarkable enhancement was attributed to the transition of the PEDOT chains from a coil to a linear or expanded coil conformation,reduction of the interplanar stacking distance,and the removal of insulating PSS with increasing the oxidation level of PEDOT,facilitating the charge transportation.This work presents an effective route for fabricating high-performance flexible conductive polymer films and wearable thermoelectric devices.

On-Chip Micro Temperature Controllers Based on Freestanding Thermoelectric Nano Films for Low-Power Electronics

Multidimensional integration and multifunctional com-ponent assembly have been greatly explored in recent years to extend Moore’s Law of modern microelectronics.However,this inevitably exac-erbates the inhomogeneity of temperature distribution in microsystems,making precise temperature control for electronic components extremely challenging.Herein,we report an on-chip micro temperature controller including a pair of thermoelectric legs with a total area of 50×50μm^(2),which are fabricated from dense and flat freestanding Bi2Te3-based ther-moelectric nano films deposited on a newly developed nano graphene oxide membrane substrate.Its tunable equivalent thermal resistance is controlled by electrical currents to achieve energy-efficient temperature control for low-power electronics.A large cooling temperature difference of 44.5 K at 380 K is achieved with a power consumption of only 445μW,resulting in an ultrahigh temperature control capability over 100 K mW^(-1).Moreover,an ultra-fast cooling rate exceeding 2000 K s^(-1) and excellent reliability of up to 1 million cycles are observed.Our proposed on-chip temperature controller is expected to enable further miniaturization and multifunctional integration on a single chip for microelectronics.

Electrodeposition and characterization of thermoelectric Bi_2Se_3 thin films

Bi2Se3 thin films were electrochemically deposited on Ti and indium tin oxide-coated glass substrates, respectively, at room temperature, using Bi（NO3）3·5H2O and SeO2 as starting materials in diluted HNO3 solution. A conventional three-electrode cell was used with a platinum sheet as a counter electrode, and a saturated calomel electrode was used as a reference electrode. The films were annealed in argon atmosphere. The influence of cold isostatic pressing before annealing on the microstructure and thermoelectric properties of the films was investigated. X-ray diffraction analysis indicates that the film grown on the indium tin oxide-coated glass substrate is pure rhombohedral Bi2Se3, and the film grown on the Ti substrate consists of both rhombohedral and orthorhombic Bi2Se3.

High temperature thermoelectric properties of highly c-axis oriented Bi_2Sr_2Co_2O_y thin films fabricated by pulsed laser deposition

High-temperature thermoelectric transport property measurements have been performed on the highly c-axis oriented Bi2Sr2Co20v thin films prepared by pulsed laser deposition on LaA1Oa （001）. Both the electric resistivity p and the seebeck coefficient S of the film exhibit an increasing trend with the temperature from 300 K-1000 K and reach up to 4.8 m. cm and 202 V/K at 980 K, resulting in a power factor of 0.85 mW/mK which are comparable to those of the single crystalline samples. A small polaron hopping conduction can be responsible for the conduction mechanism of the film at high temperature. The results demonstrate that the Bi2Sr2Co2Oy thin film has potential application has high temperature thin film thermoelectric devices,

An overview of thermoelectric films:Fabrication techniques,classification,and regulation methods

Thermoelectric materials have aroused widespread concern due to their unique ability to directly convert heat to electricity without any moving parts or noxious emissions.Taking advantages of two-dimensional structures of thermoelectric films,the potential applications of thermoelectric materials are diversified,particularly in microdevices.Well-controlled nanostructures in thermoelectric films are effective to optimize the electrical and thermal transport,which can significantly improve the performance of thermoelectric materials.In this paper,various physical and chemical approaches to fabricate thermoelectric films,including inorganic,organic,and inorganic–organic composites,are summarized,where more attentions are paid on the inorganic thermoelectric films for their excellent thermoelectric responses.Additionally,strategies for enhancing the performance of thermoelectric films are also discussed.

Facile fabrication of highly flexible,porous PEDOT:PSS/SWCNTs films for thermoelectric applications

High-performance organic composite thermoelectric(TE)materials are considered as a promising alternative for harvesting heat energy.Herein,composite films of poly(3,4-ethyienedioxythiophene):poly(styrene sulfonate)/single-walled carbon nanotubes(PEDOT:PSS/SWCNTs)were fabricated by utilizing a convenient solution mixing method.Thereafter,the as-prepared hybrid films were treated using sulfuric acid(H_(2)SO_(4))to further optimize the TE performance.Film morphological studies revealed that the sulfuric acid treated PEDOT:PSS/SWCNTs composite samples all possessed porous structures.Due to the successful fabrication of highly conductive networks,the porous nano-architecture also exhibited much more excellent TE properties when compared with the dense structure of the pristine samples.For the post-treated sample,a high power factor of 156.43μW·m^(-1)·K^(-2)can be achieved by adjusting the content of CNTs,which is approximately 3 orders of magnitude higher than that of the corresponding untreated samples(0.23μW·m^(-1)·K^(-2)).Besides,the obtained films also showed excellent mechanical flexibility,owing to the porous nanostructure and the strong p–p interactions between the two components.This work indicates that the H_(2)SO_(4) treatment could be a promising strategy for fabricating highly-flexible and porous PEDOT:PSS/SWCNTs films with high TE performances.

Interfacial behavior of a thermoelectric film bonded to a graded substrate

To improve the thermoelectric converting performance in applications such as power generation,reutilization of heat energy,refrigeration,and ultrasensitive sensors in scramjet engines,a thermoelectric film/substrate system is widely designed and applied,whose interfacial behavior dominates the strength and service life of thermoelectric devices.Herein,a theoretical model of a thermoelectric film bonded to a graded substrate is proposed.The interfacial shear stress,the normal stress in the thermoelectric film,and the stress intensity factors affected by various material and geometric parameters are comprehensively studied.It is found that adjusting the inhomogeneity parameter of the graded substrate,thermal conductivity,and current density of the thermoelectric film can reduce the risk of interfacial failure of the thermoelectric film/graded substrate system.Selecting a stiffer and thicker thermoelectric film is advantageous to the reliability of the thermoelectric film/graded substrate system.The results should be of great guiding significance for the present and upcoming applications of thermoelectric materials in various fields.

Effects of Thickness and Temperature on Thermoelectric Properties of Bi2Te3-Based Thin Films

Bi_2Te_3 thin films and GeTe/B_2Te_3 superlattices of different thicknesses are prepared on the silicon dioxide substrates by magnetron sputtering technique and thermally annealed at 573 K for 30 min. Thermoelectric（TE）measurements indicate that optimal thickness and thickness ratio improve the TE performance of Bi_2Te_3 thin films and GeTe/B_2Te_3 superlattices, respectively. High TE performances with figure-of-merit（ZT） values as high as 1.32 and 1.56 are achieved at 443 K for 30 nm and 50 nm Bi_2Te_3 thin films, respectively. These ZT values are higher than those of p-type Bi_2Te_3 alloys as reported. Relatively high ZT of the GeTe/B_2Te_3 superlattices at 300-380 K were 0.62-0.76. The achieved high ZT value may be attributed to the unique nano-and microstructures of the films,which increase phonon scattering and reduce thermal conductivity. The results indicate that Bi_2Te_3-based thin films can serve as high-performance materials for applications in TE devices.

Thermoelastic stress analysis of multilayered films in a micro-thermoelectric cooling device

This paper presents an analytical solution for the thermoelastic stress in a typical in-plane＇s thin-film micro- thermoelectric cooling device under different operating con- ditions. The distributions of the permissible temperature fields in multilayered thin-films are analytically obtained, and the characteristics, including maximum temperature dif- ference and maximum refrigerating output of the thermo- electric device, are discussed for two operating conditions. Analytical expressions of the thermoelastic stresses in the layered thermoelectric thin-films induced by the tempera- ture difference are formulated based on the theory of mul- tilayer system. The results demonstrate that, the geometric dimension is a significant factor which remarkably affects the thermoelastic stresses. The stress distributions in layers of semiconductor thermoelements, insulating and support- ing membrane show distinctly different features. The present work may profitably guide the optimization design of high- efficiency micro-thermoelectric cooling devices.

Thermoelectric effect of silicon films prepared by aluminum-induced crystallization

Aluminum-induced crystallized silicon films were prepared on glass substrates by magnetron sputtering. Aluminum was added in the silicon films intermittently by the regular pulse sputtering of an aluminum target. The amount of aluminum in the silicon films can be controlled by regulating the aluminum sputtering power and the sputtering time of the undoped silicon layer; thus, the Seebeck coefficient and electrical resistivity of the polyerystaUine silicon films can be adjusted. It is found that, when the sputtering power ratio of aluminum to silicon is 16%, both the Seebeck coefficient and the electrical resistivity decrease with the increasing amount of aluminum as expected; the Seebeck coefficient and the electrical resistivity at room temperature are 0.185-0.285 mV/K and 0.30-2.4 Ω.cm, respectively. By reducing the sputtering power ratio to 7%, however, the Seebeck coefficient does not change much, though the electrical resistivity still decreases with the amount of aluminum increasing; the Seebeck coefficient and electrical resistivity at room temperature are 0.219-0.263 mV/K and 0.26-0.80 Ω·cm, respectively.

Effect of microstructure on the thermoelectric properties of CSD-grown Bi_2Sr_2Co_2O_y thin films

Three Bi2Sr2Co2Oy thin films with different microstructures have been prepared by chemical solution deposition on LaAlO 3（001） through varying the annealing temperature.With the decrease in the annealing temperature,both the size and c-axis alignment degree of grains in the film decrease as well,leading to an increase in the film resistivity.In addition,the decrease in the annealing temperature also results in a slight increase in the Seebeck coefficient due to the enhanced energy filtering effect of the small-grain film.The nanostructured Bi2Sr2Co2Oy film with an average grain size of about 100 nm shows a power factor comparable to that of films with larger grains.Since the thermal conductivity of the nanostructured films can be depressed due to the enhanced phonon scattering by grain boundary,a higher figure of merit is expected in Bi2Sr2Co2Oy thin film with grains in nanometer size.

Hardness Measurement and Evaluation of Double-layer Films on Material Surface

A method for hardness measurement and evaluation of double-layer thin films on the material surface is proposed. Firstly, it is studied how to obtain the force-indentation response with the finite element method when the indentation is less than 100 nanometers, in which current nanoindentation experiments have no reliable accuracy. The whole hardness-displacement curve and fitted equation are obtained. At last, a formula to predict the hardness of the thin film on the material surface is derived and favorably compared with experiments.

Synthesis and thermoelectric properties of Bi-doped SnSe thin films

Bi doped n-type SnSe thin films were prepared by chemical vapor deposition(CVD)and their structure and thermoelectric properties were studied.The x-ray diffraction patterns,x-ray photoelectron spectroscopy,and microscopic images show that the prepared SnSe thin films were composed of pure SnSe crystals.The Seebeck coefficients of the Bi-doped SnSe were greatly improved compared to that of undoped SnSe thin films.Specifically,Sn_(0.99)Bi_(0.01)Se thin film exhibited a Seebeck coefficient of905.8μV·K^(-1) at 600 K,much higher than 285.5μV·K^(-1) of undoped SnSe thin film.Further first-principles calculations reveal that the enhancement of the thermoelectric properties can be explained mainly by the Fermi level lifting and the carrier pockets increasing near the Fermi level due to Bi doping in the SnSe samples.Our results suggest the potentials of the Bi-doped SnSe thin films in thermoelectric applications.

Double-layer indium doped zinc oxide for silicon thin-film solar cell prepared by ultrasonic spray pyrolysis

Indium doped zinc oxide （ZnO：In） thin films were prepared by ultrasonic spray pyrolysis on corning eagle 2000 glass substrate. 1 and 2 at.% indium doped single-layer ZnO：In thin films with different amounts of acetic acid added in the initial solution were fabricated. The 1 at.% indium doped single-layers have triangle grains. The 2 at.% indium doped single-layer with 0.18 acetic acid adding has the resistivity of 6.82 × 10^-3 Ω. cm and particle grains. The doublelayers structure is designed to fabricate the ZnO：In thin film with low resistivity （2.58 × 10^-3 Ω. cm） and good surface morphology. It is found that the surface morphology of the double-layer ZnO：In film strongly depends on the substratelayer, and the second-layer plays a large part in the resistivity of the doublewlayer ZnO：In thin film. Both total and direct transmittances of the double-layer ZnO：In film are above 80% in the visible light region. Single junction a-Si：H solar cell based on the double-layer ZnO：In as front electrode is also investigated.

Preparation of Bi_(2-x)Sb_xTe_3 thermoelectric films by electrodeposition

Bi2-xSbxTe3 thermoelectric films were electrochemically deposited from the solution containing Bi^3＋, HTeO2^＋and SbO^＋. ESEM （environmental scanning electron microscope） investigations indicated that the crystalline state of Bi2-xSbxTe3 films transformed from equiaxed crystal to dendritic crystal with the negative shift of deposition potential. XRD and EDS were used to characterize the structure and composition of the electrodeposited films. The Seebeck coefficient and the temperature dependence of the resistance of Bi2-xSbxTe3 films were measured. The results showed that the composition of the film electrodeposited at -0.5 V is Bi2-xSbxTe3 with the largest Seebeck coefficient of 213 μV·K^-1.

The transverse laser induced thermoelectric voltages in step flow growth (1-x)Pb(Mg_(1/3)Nb_(2/3))O_(3-x)PbTiO_3 thin films

This paper reports that the transverse laser induced thermoelectric voltages （LITV） axe observed for the first time in the step flow growth （1- x）PD（Mg1/3Nb2/3）O3-xPbTiO3 （PMN-PT, x = 0.20, 0.33, 0.50） thin films deposited on vicinal-cut strontium titanate single crystal substrates. Because lead magnesium niobate-lead titanate is a solid solution of lead magnesium niobate （PMN） and lead titanate （PT）, there are two types of signals. One is wide with a time response of a microsecond, and the other superimposed with the wide signal is narrow with a time response of a nanosecond. The transverse LITV signals depend on the ratio of PMN to PT drastically. Under the irradiation of 28-ns pulsed KrF excimer laser with the 248-nm wavelength, the largest induced voltage is observed in the 0.50Pb（Mg1/3Nb2/3）O3-0.50 PbTiO3 films. Moreover, the effects of film thickness, substrates, and tilt angles of substrates are also investigated.

Electrochemical Deposition and Optimization of Thermoelectric Nanostructured Bismuth Telluride Thick Films

Bismuth telluride thick films are suitable for thermoelectric (TE) devices covering large areas and operating at small-to-moderate temperature differences (20 - 200 K). High efficiency and high coefficient of performance (COP) are expected to be achieved by using thick films in some cooling applications. Bismuth telluride thick films fabrication have been achieved with Galvanostatic and Potentionstatic deposition. Stoichiometric bismuth telluride thick film was obtained by Galvanostatic deposition at current density of 3.1 mAcm-2. Bismuth telluride films with average growth rate of 10 μmh-1 and different composition were obtained. Effects of current density and composition of electrolyte in Galvanostatic deposition were studied. The current density affected the film compactness, where films deposited at lower current density were more compact than those deposited at higher current density. The morphology of the films did not depend on the current density, but chemical composition was observed when different composition of electrolyte was used. Effects of distance between electrodes, composition of electrolyte solution, and stirring in Potentionstatic deposition were studied. The shorter the distance between electrodes, the higher the electric field, thus the higher current density was applied and the deposited film was less compact. The current density increased more rapidly with stirring during electrodeposition which leads to less compact film. Through this study, films electrode-posited from solution containing 0.013 M Bi(NO3)3.5 H2O, 0.01 M TeO2 and 1 M HNO3 at 3.1 mA cm-2 for 6 hours without stirring and with interelectrode distance of 4.5 cm were free-standing with average film thickness of 60 μm and optimum film composition of Bi2Te3. The crystallite size of the later films was found to be around 4.3 nm using Scherrer’s equation from XRD patterns. Also, negative Seebeck coefficient for the same samples was revealed with an average value of -82 μV.K-1.

Thermoelectric Transport by Surface States in Bi2Se3-Based Topological Insulator Thin Films

We develop a tractable theoretical model to investigate the thermoelectric （TE） transport properties of surface states in topological insulator thin films （TITFs） of Bi2Sea at room temperature. The hybridization between top and bottom surface states in the TITF plays a significant role. With the increasing hybridization-induced surface gap, the electrical conductivity and electron thermal conductivity decrease while the Seebeck coefficient increases. This is due to the metal-semiconductor transition induced by the surface-state hybridization. Based on these TE transport coefficients, the TE figure-of-merit ZT is evaluated. It is shown that ZT can be greatly improved by the surface-state hybridization. Our theoretical results are pertinent to the exploration of the TE transport properties of surface states in TITFs and to the potential application of Bi2Sea-based TITFs as high-performance TE materials and devices.

Proposal and Verification of Simultaneous Measurement Method for Three Thermoelectric Properties with Film-Type Thermocouple Probe

A new simultaneous measurement method for the measurement of the three thermoelectric properties with a film-type thermocouple probe was proposed. Seebeck coefficient was measured using the steady-state condi-tion of the differential method. The electrical resistivity was measured us-ing the four-probe method and the thermal diffusivity is measured using the periodic heating method. The effectiveness of the proposed method was verified using constantan as a reference material. After describing the effectiveness of the method, the measurement of three thermoelectric properties of Bi0.3Sb1.7Te3, which is a thermoelectric material, was per-formed.