Thermoelectric properties of Al-doped ZnO: experiment and simulation

Advancement in doping other elements, such as Ce, Dy, Ni, Sb, In and Ga in ZnO^[1], have stimulated great interest for high-temperature thermoelectric application. In this work, the effects of Al-doping in a ZnO system on the electronic structure and thermoelectric properties are presented, by experiment and calculation.Nanosized powders of Zn_1-xAl_xO (x=0, 0.01, 0.02, 0.03 and 0.06) were synthesized by hydrothermal method. From XRD results, all samples contain ZnO as the main phase and ZnAl₂O₄ (spinel phase) peaks were visible when Al additive concentrations were just 6 at%. The shape of the samples changed and the particle size decreased with increasing Al concentration. Seebeck coefficients, on the other hand, did not vary significantly. They were negative and the absolute values increased with temperature. However, the electrical resistivity decreased significantly for higher Al content.The electronic structure calculations were carried out using the open-source software package ABINIT^[2], which is based on DFT. The energy band gap, density of states of Al-doped ZnO were investigated using PAW pseudopotential method within the LDA+U. The calculated density of states was then used in combination with the Boltzmann transport equation^[3] to calculate the thermoelectric parameters of Al-doped ZnO. The electronic band structures showed that the position of the Fermi level of the doped sample was shifted upwards in comparison to the undoped one. After doping Al in ZnO, the energy band gap was decreased, Seebeck coefficient and electrical conductivity were increased.Finally, the calculated results were compared with the experimental results. The good agreement of thermoelectric properties between the calculation and the experimental results were obtained.     

First-Principles Study of the Electronic Structure and Thermoelectric Properties of Al-Doped ZnO

ZnO materials doped with elements such as Al, Ga, etc. are of great interest for high-temperature thermoelectric applications. In this work, the effects of Al doping on the electronic structure and thermoelectric properties of the ZnO system are presented. The energy band structure and density of states of Al-doped ZnO were investigated using the projector-augmented plane wave pseudopotential method within the local density approximation. The calculated energy band structure was then used in combination with the Boltzmann transport equation to calculate the thermoelectric parameters of Al-doped ZnO. The electronic structure calculation showed that the position of the Fermi level of the doped sample was shifted to a higher energy level compared with the undoped material. The conduction band near the Fermi energy was a combination of hybridized Zn sp-orbitals and Al s-orbital. The calculated thermoelectric properties were compared with the experimental results, showing some agreement. For the Al-doped ZnO system, the Seebeck coefficient was shown to be negative and its absolute value increased with temperature. The electrical conductivity and electronic thermal conductivity followed the trend of the experimental results.     

Optical and electrical properties of epitaxial (Mg,Cd)xZn1−xO, ZnO, and ZnO:(Ga,Al) thin films on c-plane sapphire grown by pulsed laser deposition

A consistent set of epitaxial, n-type conducting ZnO thin films, nominally undoped, doped with Ga or Al, or alloyed with Mg or Cd, was grown by pulsed laser deposition (PLD) on single-crystalline c-plane sapphire (0 0 0 1) substrates, and characterized by Hall measurement, and UV/VIS optical transmission spectroscopy.The optical band gap of undoped ZnO films at nearly 3.28 eV was shifted by alloying with Mg up to 4.5 eV and by alloying with Cd down to 3.18 eV, dependent on the alloy composition. In addition, highly doped ZnO:Al films show a blue-shifted optical absorption edge due to filling of electronic states in the conduction band.The Hall transport data of the PLD (Mg,Zn,Cd)O:(Ga,Al) thin films span a carrier concentration range of six orders of magnitude from 3 × 10¹⁴ to 3 × 10²⁰ cm⁻³, which corresponds to a resistivity from 5 × 10⁻⁴ to 3 × 10³ Ω cm. Structurally optimized, nominally undoped ZnO films grown with ZnO nucleation and top layer reached an electron mobility of 155 cm²/V s (300 K), which is among the largest values reported for heteroepitaxial ZnO thin films so far.Finally, we succeeded in combining the low resistivity of ZnO:Ga and the band gap shift of MgZnO in MgZnO:Ga thin films. This results demonstrate the unique tunability of the optical and electrical properties of the ZnO-based wide-band gap material for future electronic devices.     

Photoconductive ZnO Films Printed on Flexible Substrates by Inkjet and Aerosol Jet Techniques

Zinc oxide (ZnO) thin films have remarkable versatility in sensor applications. Here, we report simple ink synthesis and printing methods to deposit ZnO photodetectors on a variety of flexible and transparent substrates, including polyimide (Kapton), polyethylene terephthalate, cyclic olefin copolymer (TOPAS), and quartz. X-ray diffraction analysis revealed the dependence of the film orientation on the substrate type and sintering method, and ultraviolet–visible (UV–Vis) absorption measurements revealed a band edge near 380 nm. van der Pauw technique was used to measure the resistivity of undoped ZnO and indium/gallium-codoped ZnO (IGZO) films. IGZO films showed lower resistivity and larger average grain size compared with undoped ZnO films due to addition of In³⁺ and Ga³⁺, which act as donors. A 365-nm light-emitting diode was used to photoirradiate the films to study their photoconductive response as a function of light intensity at 300 K. The results revealed that ZnO films printed by aerosol jet and inkjet techniques exhibited five orders of magnitude photoconductivity, indicating that such films are viable options for use in flexible photodetectors.     

Thermoelectric Properties of Nanograined ZnO

Bulk ZnO with a grain size of 20 nm was successfully obtained by pulsed electric current sintering. The crystalline size was almost identical to that of the raw particles, because the sintering temperature was as low as 200°C. A pressure of 500 MPa effectively enhanced densification, leading to a relative density of >90% at 200°C. The small grain size led to a low thermal conductivity of 3 W/m K at room temperature, due to enhanced boundary scattering. The Seebeck coefficient was higher than that of micrograined ZnO with similar Ga doping (0.3 at.% Ga). However, the resistivity was increased by more than 1000 times. The temperature dependence of conductivity showed thermally activated conduction behavior, while that of micrograined ZnO exhibited metallic-like behavior. The thermoelectric properties suggest that a carrier trap in the nanograined ZnO hinders carrier transport. Surface modification of the ZnO nanoparticles by heat treatment in H₂ resulted in observable photoluminescence which was quenched in the starting nanoparticles, and led to a decrease in the resistivity of the sintered bulk, which indicates that control of surface defects on the nanoparticles is crucial for enhancement of the thermoelectric properties of nanograined ZnO.     

Low-resistance Ti/Al ohmic contact on undoped ZnO

We report a low-resistance ohmic contact on undoped ZnO using a promising contact scheme of Ti/Al. Specific-contact resistivity, as low as 9.0 × 10^?7 ωcm², was obtained from the Ti (300 Å)/Al (3,000 Å) contact annealed at 300°C. It was found that TiO was produced, and the atomic ratio of Zn/O was dramatically increased after annealing at 300°C. This provides the evidence that a number of oxygen vacancies, acting as donors for electrons, were produced below the contact. This leads to the increase of electron concentration via the reduction of contact resistivity.     

Mg and Al co-doping of ZnO thin films: Effect on ultraviolet photoconductivity

Thin films of Zinc Oxide were deposited by the sol-gel technique on glass substrates. The films were doped with Al, Mg or co-doped with both by introduction of appropriate compounds in the solution before dip-coating and annealing in air at 500 °C. Energy Dispersive X-Ray Spectroscopy was employed to measure the dopant incorporation. X-ray diffraction studies indicate that Mg doping increases grain size, while Al doping reduces it. Photoluminescence (PL) measurements indicate that undoped and Al-doped films show, along with a broad near band-edge (NBE) peak, additional peaks at longer wavelengths related to various defect states. However Mg doped films show only a sharp NBE peak, which is blue shifted compared to undoped ZnO, and there are no prominent sub band gap luminescence peaks. This is also the case for Mg and Al co-doped ZnO samples, provided the Mg content is low. Photocurrent measurements were carried out using silver contacts using a De source under atmospheric conditions. Undoped and Mg doped ZnO films showed high resistances and low photocurrent levels. With low Al doping, both the dark current and the photocurrent increase significantly, but the films show very long photocurrent transients. With optimized concentration of Mg/Al co-doping in ZnO, the photocurrent increased by ~98 times compared to ZnO films doped only with Mg. Simultaneously, the photocurrent transients became ~44 times faster than ZnO films doped only with Al.     

Effects of the ZnO buffer layer and Al proportion on AZO film properties

To evaluate the influence of the ZnO buffer layer and Al proportion on the properties of ZnO: Al (AZO)/ZnO bi-layer films, a series of AZO/ZnO films are deposited on the quartz substrates by electron beam evaporation. The X-ray diffraction measurement shows that the crystal quality of the films is improved with the increase of the film thickness. The electrical properties of the films are investigated. The carrier concentration and Hall mobility both increase with the increase of buffer layer thickness. However, the resistivity reaches the lowest at about 50 nm-thick buffer layer. The lowest resistivity and the maximum Hall mobility are both obtained at 1 wt% Al concentration. But the optical transmittance of all the films is greater than 80% regardless of the buffer layer thickness with Al concentration lower than 5 wt% in the visible region.     

Theoretical and experimental investigations of the thermoelectric properties of Al-, Bi- and Sn-doped ZnO

In this paper, the thermoelectric properties of ZnO doped with Al, Bi and Sn were investigated by combining experimental and theoretical methods. The average Seebeck coefficient of Bi doped ZnO over the measured temperature range is improved from −90 to −497 μV/K. However, segregation of Bi₂O₃ in ZnO:Bi sample, confirmed by FESEM, lead to enormous grain growth and low electrical conductivity, which makes Bi is not a good dopant to improve ZT value of ZnO. As a 4+ valence cation, Sn doping actually show an increase in carrier concentration to 10²⁰ cm⁻³, further enhancing the electrical conductivity. Unfortunately, the Seebeck coefficient of ZnO:Sn samples is even lower than pure ZnO sample, which lead to a low ZT value. As for ZnO:Al sample, with nearly no change in lattice thermal conductivity, electrical conductivity and Seebeck coefficient were both enhanced. Threefold enhancement in ZT value has been achieved in ZnO:Al sample at 760 °C compared with pure ZnO.     

本征和Al3+掺杂ZnO薄膜的特性研究

采用溶胶-凝胶方法在载玻片衬底上制备了本征及不同Al3+掺杂浓度的ZnO:Al薄膜,利用X射线衍射(XRD)、原子力显微镜,紫外-可见光吸收光谱及霍尔效应研究了Al3+掺杂浓度对ZnO:Al薄膜结构和光电性能的影响。结果显示,ZnO:Al薄膜为六角纤锌矿晶体结构,具有很高的沿c轴的(002)择优取向,Al3+掺杂并没有改变ZnO的晶体结构,只是Al取代了Zn;掺杂前后薄膜样品均在ZnO带边吸收的位置有较强的吸收而在可见光范围吸收较小;并且当Al3+掺杂浓度为1.5%(摩尔百分比)时所获得的ZnO:Al薄膜具有最小的电阻率,为26Ωcm。     

Properties of nanostructured Al doped ZnO thin films grown by spray pyrolysis technique

Aluminium doped zinc oxide thin films were deposited on glass substrate by using spray pyrolysis technique. The X-ray diffraction study of the films revealed that the both the undoped and Al doped ZnO thin films exhibits hexagonal wurtzite structure. The preferred orientation is (002) for undoped and up to 3 at % Al doping, further increase in the doping concentration to 5 at % changes the preferred orientation to (101) direction. The surface morphology of the films studied by scanning electron microscope, reveal marked changes on doping. Optical study indicates that both undoped and Al doped films are transparent in the visible region. The band gap of the films increased from 3.24 to 3.36 eV with increasing Al dopant concentration from 0 to 5 at % respectively. The Al doped films showed an increase in the conductivity by three orders of magnitude with increase in doping concentration. The maximum value of conductivity 106.3 S/cm is achieved for 3 at % Al doped films.     

快速热退火前后ZnO及ZnO/Al薄膜性质的研究

鉴于直流反应溅射制ZAO膜对反应条件敏感,研究发现,经快速热退火(RTA)处理能放宽对反应条件的要求。实验中ZnO及ZnO/Al薄膜用直流反应磁控溅射法制备。选用金属Zn及金属合金Zn/Al靶。经快速热退火(RTA)后,通过XRD,UV-VIS-NIR分光光度计、四探针测方电阻等,研究了经不同温度RTA后ZnO及ZnO/Al薄膜的结晶状况、方电阻、电阻率、可见光透过率等的变化。对传统热退火和RTA进行了比较:经RTA600℃后电阻率减小5~9个数量级,达1×10–3·cm。     

氧流量对绒面氧化锌透明导电薄膜性能的影响

利用中频脉冲磁控溅射工艺制备了低阻高透过率的ZAO薄膜,用湿法腐蚀的方法将制备的平面ZAO薄膜在0.5%的稀盐酸中浸泡一定时间得到绒面ZAO薄膜.研究了氧流量对腐蚀后薄膜表面形貌的影响.结果表明,随着氧流量的增大腐蚀后薄膜的表面形貌由花瓣状逐渐为适合太阳电池的陨石坑状,在氧流量为3.6 sc-cm时(氩流量为12 sccm)得到最好的绒面ZAO薄膜,继续增加氧流量,薄膜开始变得粗糙,说明薄膜的表面形貌又变差.     

Thermoelectric Performance of ZnO:Al/ZnO:(Al,In) Quantum Well Multilayer Structures as a Function of Indium Composition and Band-Gap Offset at High Operating Temperatures

This study investigates the thermoelectric (TE) power factor for radiofrequency (RF)-sputtered n-type ZnO:Al/ZnO:(Al,In) multilayer quantum wells (QW) and the dependence on band-gap offset at high operating temperatures. The structures are 50 periods of 10-nm-thick barrier and well layers. The TE power factors for all films are promising (>20?×?10^?4?W/m²?K); however, a decline in electronic transport is evident for each of the doped wells over a specific range of operating temperatures. This supports the need for optimum doping levels for a specific operating temperature range; e.g., 2?at.%, 5?at.%, and 8?at.% indium are optimum at 300?K to 600?K, 600?K to 725?K, and >725?K, respectively. A model has also been developed to calculate the QW electronic transport as a function of temperature and band-gap offset, which is subsequently related to doping concentration. This model confirms a loss in electrical conductivity due to charge carriers gaining enough kinetic energy to overcome the QW barrier, which results in multilayer hopping across well?Cbarrier interfaces. In addition, film microstructure and interface roughness have been determined by x-ray and spectroscopy techniques.     

硫掺杂对ZnO热电性能的影响

采用固相反应法制备了ZnO1-xSx块体材料(0≤x≤0.05);通过对样品X射线衍射谱(XRD)、电导率和Seebeck系数的测量,研究了S掺杂对ZnO晶体结构及热电性能的影响。结果表明:所有试样均为六方纤锌矿结构。在573 K时,ZnO1-xSx(0相似文献   

Influence of Thermal Aging Phenomena on Thermoelectric Properties of Al-Substituted ZnO

The thermoelectric properties and stability of Al-substituted ZnO as a potential high-temperature n-type material were studied in heating?Ccooling cycles. Zn_1?x Al _x O (x?=?0.02, 0.06) was prepared by soft chemistry and solid-state reaction synthesis methods. Cycling during the thermoelectric measurement leads to an increase of the electrical resistivity and Seebeck coefficient values. The reason for this aging phenomenon can be assigned to a change in composition due to oxygen uptake along with modification in the defect concentrations. The aging is enhanced if the cycling is performed in oxygen. ZT value of 0.21 is reached at 1275?K for samples with 2% Al substitution made by soft chemistry synthesis.     

Electrical and optical properties of ZnO/Si heterojunctions as a function of the Mg dopant content

Undoped and Mg-doped ZnO thin films prepared by a sol–gel process were deposited on p-Si and glass substrates via spin coating. The electrical and optical properties of the films were investigated. Atomic force microscopy images revealed that the ZnO films are formed from fibers consisting of nanoparticles. The electrical conductivity mechanism of the films was investigated. The I–V characteristics of Al/ZnO/p-Si samples showed rectification behavior with a rectification ratio that depended on the applied voltage and the Mg doping ratio. ZnO/p-Si heterojunction diodes exhibited non-ideal behavior with an ideality factor greater than unity that could be ascribed to the interfacial layer, interface states, and series resistance. The barrier height for undoped and Mg-doped ZnO/p-Si diodes was in the range 0.78–0.84 eV. The results demonstrate that the electrical properties of ZnO/p-Si heterojunction diodes are controlled by the Mg dopant content and suggest that the optical bandgap of these ZnO films can be tuned using the Mg level.     

磁控溅射制备ZnO薄膜及其掺杂的研究

利用磁控溅射制备了纯ZnO薄膜,并在NH3O-2A-r气氛中溅射Zn靶实现了ZnO薄膜的N掺杂;利用双靶共溅的方法分别制备了Al掺杂和N+Al掺杂样品。原子力显微镜(AFM)观察显示各ZnO薄膜样品具有较好的晶粒分布,退火处理能够显著提高薄膜的结构状态,N+Al共掺杂样品具有较好的表面平整度;在438cm-1附近观察到了喇曼谱特征峰;透射光谱揭示了激子的吸收特征和掺杂样品的吸收边向短波方向移动;发射光谱测试表明,掺杂样品比未掺杂样品有更强的紫外发射;同时分析了ZnO薄膜的掺杂机理。     

Title: Using Alignment and 2D Network Simulations to Study Charge Transport Through Doped ZnO Nanowire Thin Film Electrodes

Factors affecting charge transport through ZnO nanowire mat films were studied by aligning ZnO nanowires on substrates and coupling experimental measurements with 2D nanowire network simulations. Gallium doped ZnO nanowires were aligned on thermally oxidized silicon wafer by shearing a nanowire dispersion in ethanol. Sheet resistances of nanowire thin films that had current flowing parallel to nanowire alignment direction were compared to thin films that had current flowing perpendicular to nanowire alignment direction. Perpendicular devices showed ～5 fold greater sheet resistance than parallel devices supporting the hypothesis that aligning nanowires would increase conductivity of ZnO nanowire electrodes. 2‐D nanowire network simulations of thin films showed that the device sheet resistance was dominated by inter‐wire contact resistance. For a given resistivity of ZnO nanowires, the thin film electrodes would have the lowest possible sheet resistance if the inter‐wire contact resistance was one order of magnitude lower than the single nanowire resistance. Simulations suggest that the conductivity of such thin film devices could be further enhanced by using longer nanowires.     

The High-Temperature Thermoelectric Properties of Polycrystalline Ba8Ga x Al y Si46−x−y Type-I Clathrates

Thermoelectric materials suitable for practical thermoelectric power generators should, ideally, be based on light elements, for example Si and Al, which are abundantly available. For this reason, silicon clathrate compounds in which both Ga and Al were substituted for Si were synthesized and their thermoelectric properties were investigated. The temperature-dependent electrical resistivity of the samples indicated their metallic nature, and their negative Seebeck coefficient suggested that charge transport in the samples was mainly through electron transport. The maximum absolute value of the Seebeck coefficient achieved was ?180 μV/K at 1040 K for Ba_7.90Ga_13.8Al_2.29Si_30.0. Thus, these materials have potential for use in practical thermoelectric power generators.