First-principles study on the effect of high In doping on the conductivity of ZnO

Based on the density functional theory （DFT）, using first-principles plane-wave ultrasoft pseudopotential method, the models of the unit cell of pure ZnO and two highly In-doped supercells of Zn0.9375In0.0625O and Zn0.875In0.125O are constructed, and the geometry optimizations of the three models are carried out. The total density of states （DOS） and the band structures （BS） are also calculated. The calculation results show that in the range of high doping concentration, when the doping concentration is hihger than a specific value, the conductivity decreases with the increase of the doping concentration of In in ZnO, which is in consistence with the change trend of the experimental results.

First-principles Studies on Electronic Structures of Ga-doped ZnO and ZnS

First-principles calculations have been performed to clarify the differences of the electronic structures of Ga-doped ZnO and ZnS. Results show the local density approximation and local density approximation＋U calculations are in good qualitative agreement with each other. After doping, impurity states appear near the Fermi level in both ZnO and ZnS cases. When ZnO is doped, the impurity states are delocalized in the whole conduction band. On the contrary, when ZnS is doped, though the p state of Ga is also delocalized, the s state is localized near the Fermi level. Partial charge density distributions of the frontier orbital show the same information. After an exchange of the crystal structures of ZnO and ZnS, results remain unchanged. The localized Ga s state accounts for the bad electrical properties of Ga-doped ZnS.

First-Principle Studies on Conductive Behaviors of P-Type ZnO Codoped by N and B

Using a first-principle method, the electronic structures and the impurity formation energy of ZnO, ZnO （N）, ZnO （N＋B）, and ZnO （2N＋B） have been calculated, based on which the feasibility to obtain p-type ZnO ＆ discussed. According to the results, when ZnO is single doped by N, the acceptor level is deep, and the formation energy is negative, so the ideal p-type ZnO can not be obtained by this way. On the contrary, when 2N＋B are codoped into ZnO, the acceptor level becomes much lower, and the formation energy is positive, so it is a better way to obtain p-type ZnO.

Comparisons of ZnO codoped by group IIIA elements (Al,Ga,In) and N:a first-principle study

The electronic structures and effective masses of the N mono-doped and Al N, Ga-N, In-N codoped ZnO system have been calculated by a first-principle method, and comparisons among different doping cases are made. According to the results, the impurity states in the codoping cases are more delocalised compared to the N mono-doping case, which means a better conductive behaviour can be obtained by codoping. Besides, compared to the Al-N and Ga-N codoping cases, the hole effective mass of In-N codoped system is much smaller, indicating the p-type conductivity can be more enhanced by In N codoping

First-principles calculation of electronic structure of Mg_xZn_(1-x)O codoped with aluminium and nitrogen

Aiming at developing p-type semiconductors and modulating the band gap for photoelectronic devices and band engineering, we present the ab initio numerical simulation of the effect of codoping ZnO with Al, N and Mg on the crystal lattice and electronic structure. The simulations are based on the Perdew-Burke-Ernzerhof generalised-gradient approximation in density functional theory. Results indicate that electrons close to the Fermi level transfer effectively when Al, Mg, and N replace Zn and O atoms, and the theoretical results were consistent with the experiments. The addition of Mg leads to the variation of crystal lattice, expanse of energy band, and change of band gap. These unusual properties are explained in terms of the computed electronic structure, and the results show promise for the development of next-generation photoconducting devices in optoelectronic information science and technology.

Effect on Defect in N or F-Doped Ferromagnetic Zn_1-xCu_xO: First-Principles Study

We investigated the electronic and magnetic properties for O or Zn defect of (Cu, N) or (Cu, F)-co- doped ZnO with the concentration of 2.77% - 8.33% by using the first-principles calculations. The ferromagnetic coupling of Cu atoms in (Cu, N)-codoped ZnO can be attributed to the hole-mediated double-exchange through the strong 2p-3d coupling between Cu and neighboring O (or N) atoms. The ferromagnetism in Cu-doped ZnO is controllable by changing the carrier density. The Cu magnetic moment in low Cu concentration (2.77%) is increased by the N-doping, while for the F-doping it decreases. For two Cu atoms of Zn0.9445Cu0.0555O with O vacancy, the antiferromagnetic state is more energetically favorable than the ferromagnetic state.

Effect of band gap energy on the electrical conductivity in doped ZnO thin film

The transparent conductive pure and doped zinc oxide thin films with aluminum, cobalt and indium were deposited by ultrasonic spray technique on glass substrate at 350 ℃. This paper is to present a new approach to the description of correlation between electrical conductivity and optical gap energy with dopants＇ concentration of A1, Co and In. The correlation between the electrical and optical properties with doping level suggests that the electrical conductivity of the films is predominantly estimated by the band gap energy and the concentrations of A1, Co and In. The measurement in the electrical conductivity of doped films with correlation is equal to the experimental value, the error of this correlation is smaller than 13%. The minimum error value was estimated in the cobalt-doped ZnO thin films. This result indicates that such Co-doped ZnO thin films are chemically purer and have far fewer defects and less disorder owing to an almost complete chemical decomposition.

First-principles Study on Neutral Nitrogen Impurities in Zinc Oxide

The atomic geometries, electronic structures, and formation energies of neutral nitrogen im- purities in ZnO have been investigated by first-principles calculations. The nitrogen impuri- ties are always deep acceptors, thus having no contributions to p-type conductivity. Among all the neutral nitrogen impurities, nitrogen substituting on an oxygen site has the lowest formation energy and the shallowest acceptor level, while nitrogen .substituting on a zinc site has the second-lowest formation energy in oxygen-rich conditions. Nitrogen interstitials are unstable at the tetrahedral site and spontaneously relax into a kick-out configuration. Though nitrogen may occupy the octahedral site, the concentrations will be low for the high formation energy. The charge density distributions in various doping cases are discussed, and self-consistent results are obtained.

Tailoring the structural and magnetic properties of Cu-doped ZnO by c-axis pressure

The structural and magnetic properties of the Cu-doped ZnO（ZnO：Cu） under c-axis pressure were studied using first-principle calculations. It was found that the ZnO：Cu undergoes a structural transition from Wurtzite to Graphite-like structure at a c-axis pressure of 7–8 GPa. This is accompanied by an apparent loss of ferromagnetic stability, indicating a magnetic transformation from a ferromagnetic state to a paramagnetic-like state. Further studies revealed that the magnetic instability is closely related to the variation in crystalline field originated from the structural transition, which is in association with the overlapping of spin–charge density between the Cu^2＋ and adjacent O^2-.

A comparison of transmittance properties between ZnO∶Al films for transparent conductors for solar cells deposited by sputtering of AZO and cosputtering of AZO/ZnO

Aluminum-doped zinc oxide (AZO) thin films were deposited on sapphire (002) and glass substrates by two different sputtering techniques radio frequency magnetron cosputtering of AZO and ZnO targets and sputtering of an AZO target. The dependence of the photoluminescence (PL) and transmittance properties of the AZO films deposited by cosputtering and sputtering on the AZO/ZnO target power ratio, R and the O2/Ar flow ratio, r were investigated, respectively. Only a deep level emission peak appears in the PL spectra of cosputtered AZO films whereas both UV emission and deep level emission peaks are observed in the PL spectra of sputtered AZO films. The absorption edges in the transmittance spectra of the AZO films shift to the lower wavelength region as R and r increase. Effects of crystallinity, surface roughness, PL on the transmittance of the AZO films were also explained using the X-ray diffraction (XRD), atomic force microscopy (AFM), and PL analysis results.

First-principles calculations on magnetic property of Cu-doped Zn O tuned by Na and Al dopants

The effect of a second dopant on the magnetic property of Cu-doped ZnO by first-principles calculations based on the density functional theory was studied. It is found that the Cu-doped ZnO shows ferromagnetism due to the hybridization between Cu-3d and O-2p orbitals. When Na is introduced to the Cu-doped ZnO system, Cu cations tend to take on a bivalent state. Therefore, the magnetic moments on both Cu and coordinated oxygen sites increase due to Na doping. On the contrary, the magnetic moments decrease dramatically in the （Cu, A1） co-doped ZnO, which can be attributed to the fully occupied 3d states of Cu＋ and O-2p states.

ZnO纳米粉体的液相掺杂制备策略与应用

【目的】探讨制备结构形貌可控、导电性良好的ZnO纳米粉体策略。【研究现状】掺杂ZnO纳米粉体的液相制备策略,包括两步合成法前驱体转化和一步合成法原位掺杂,两步合成法包括沉淀法、溶胶‒凝胶法、恒流电解法等,一步合成法包括高压加热法、常压加热法等;总结ZnO纳米粉体掺杂导电机制,以及ZnO纳米粉体在透明导电氧化物膜、抗静电复合材料、防静电热控涂层方面的应用。【结论与展望】认为离子掺杂已成为调控晶体材料性能的有效手段,通过有效的掺杂可以对材料的性能进行连续地调控,从而获得适应具体应用场景的高性能材料;提出导电掺杂能拓宽ZnO应用,应探索制备大批量ZnO纳米粉体材料的液相掺杂策略,形成液相路线对于ZnO纳米颗粒的形貌和导电性的可调,提高液相法杂质离子的掺杂效率、掺杂均匀性及批次稳定性,形成分子乃至原子层面对于液相合成过程和掺杂元素分布的有效分析手段,深入探讨合成和掺杂机制。

Low-temperature deposition of transparent conducting Mn-W co-doped ZnO thin films

Mn-W co-doped ZnO（ZMWO） thin films with low resistivity and high transparency were successfully prepared on glass substrate by direct current（DC） magnetron sputtering at low temperature.The sputtering power was varied from 65 to 150 W.The crystallinity and resistivity of ZMWO films greatly depend on sputtering power while the optical transmittance and optical band gap are not sensitive to sputtering power.All the deposited films are polycrystalline with a hexagonal structure and have a preferred orientation along the c-axis perpendicular to the substrate.Considering the crystallinity and the electrical and optical properties,we suggest that the optimal sputtering power in this experiment is 90 W and,at this power,the ZMWO film has the lowest resistivity of 9.8×10^（-4）Ω.cm with a high transmittance of approximately 89%in the visible range.

Effect of Doped Boron on the Properties of ZnO Thin Films Prepared by Sol-gel Spin Coating

Transparent conductive boron-doped ZnO thin films were prepared by sol-gel spin coating method. The effect of doped boron concentration on the properties of the films was systematically discussed. The films were characterized by X-ray diffraction, atomic force microscopy, spectrophotometry, and Hall effect measurement system. All the doped and undoped ZnO films were of a single hexagonal structure, and showed a preferred orientation of （002）. The particle size and surface roughness of the films decreased with increased doped boron concentration. All the films exhibited an average transmittance of approximate 90% in visible-light region and an energy gap of about 3.3 cV. The maximum carrier concentration, the highest carrier mobility and the lowest resistivity were observed at a doped boron concentration of 0.5%（molar fraction）. Based on these results, we suggested that the saturation concentration of doped boron in ZnO film is 0.5%（molar fraction）.

Ga Al In掺杂ZnO电子结构的第一性原理计算

计算了Ga、Al、In掺杂ZnO体系电子结构,分析了掺杂对ZnO晶体的结构、能带、电子态密度、差分电荷分布的影响。所有计算,都是基于密度泛函理论(DFT)框架下的第一性原理平面波超软赝势方法。计算结果表明:在导带底引入了大量由掺杂原子贡献的导电载流子(Ga:2.57×1021cm–3;Al:2.58×1021cm–3;In:2.53×1021cm–3),明显提高了体系的电导率。同时,光学带隙展宽,且向低能方向漂移,可作为优良的透明导电薄膜材料。

Sol-Gel法制备ZnO∶Al透明导电薄膜

采用Sol Gel工艺在普通载玻片上制备出C轴择优取向性、高可见光透过率以及高电导率的Al3+离子掺杂的ZnO透明导电薄膜。利用SEM、XRD等分析手段对薄膜进行了表征。研究结果表明 :所制备的薄膜为纤锌矿型结构 ,表面平整、致密。通过标准四探针法及UVS透射光谱详细研究了Al3+ 离子掺杂的ZnO薄膜的电学与光学性能。实验发现 ,当Al3+ 离子掺杂浓度为 0 8%时 ,前处理温度为 40 0℃ ,退火温度为 5 5 0℃ ,真空退火温度为 5 5 0℃时 ,薄膜具有较好的导电性 ,电阻率为 3 0 3× 10 - 3Ω·cm ,其在可见光区的透过率超过 80 %。

气溶胶辅助化学气相沉积制备Al掺杂ZnO透明导电薄膜

采用气溶胶辅助化学气相沉积(AACVD)法在玻璃衬底上制备了Al掺杂ZnO(AZO)薄膜.研究了Al掺杂(2at%～8at%)对ZnO薄膜结构及光电性能的影响.利用XRD、SEM、EDAX、紫外可见分光光度计等手段对样品进行测试.结果表明,制备的所有AZO薄膜均具有纤锌矿结构,不具有沿c轴方向的择优取向,XRD图谱中未观察出Al的相关分相.在可见光范围内,AZO薄膜的平均透过率大于72%,光学禁带宽度随Al掺杂量的增加而变窄.同时根据四探针技术所得的数据得知:Al的掺杂导致薄膜方块电阻的变化,随着Al掺杂量的增加,方块电阻有明显变小的现象,掺杂6at%Al的AZO薄膜具有最低方块电阻(18Ω/□).

膜厚对Zr,Al共掺杂ZnO透明导电薄膜结构和光电性能的影响

采用直流磁控溅射法在玻璃衬底上制备出Zr,Al共掺杂ZnO(AZZO)透明导电薄膜。用XRD和SEM分析和观察了薄膜样品的组织结构和表面形貌。研究表明:制备的AZZO透明导电薄膜为六角纤锌矿结构的多晶薄膜,且具有c轴择优取向。另外还研究了薄膜的结构、光学和电学性质随薄膜厚度的变化关系。当薄膜厚度为843nm时,电阻率具有最小值1.18×10-3Ω.cm,在可见光区(500～800nm)平均透过率超过93%。

In掺杂和退火对磁控溅射制备ZnO薄膜的结构和光电性质的影响

用射频磁控溅射技术在石英玻璃衬底上制备出ZnO和In掺杂的ZnO(ZnO∶In)薄膜,研究了In的掺杂和退火对薄膜的结构和光电性质的影响。所制备的薄膜为纤锌矿结构的ZnO相,In的掺杂有利于ZnO薄膜的c轴择优生长,并且使其表面更加致密平整,退火提高了薄膜的结晶行为,但使得薄膜的表面有部分团聚形成。由于In3+替代了Zn2+,提供了一个多余的电子,ZnO薄膜的电阻率从28.9Ω.cm降低到4.3×10-3Ω.cm。由于载流子浓度的增加和晶格尺寸的拉长,In的掺杂使得ZnO薄膜的禁带宽度增加;空气中退火后薄膜的载流子浓度降低和晶格尺寸的减小,使得禁带宽度降低。ZnO薄膜在可见光范围的透光率在90%以上,受In的掺杂和退火的影响不大。室温下用325 nm的激发光源测试了样品的光致发光(PL)谱,发现In的掺杂对薄膜的PL谱影响不大,而退火后的ZnO薄膜在446 nm处的蓝光发射明显增强,更适合于作为蓝色发光器件。

溅射功率对Zr,Al共掺杂ZnO薄膜结构和性能的影响

室温下,采用直流磁控溅射法,在载玻片衬底上制备出了Zr,Al共掺杂ZnO(AZZO)透明导电薄膜。研究了溅射功率对薄膜的组织结构、表面形貌和光电学性能的影响。结果表明,制备的AZZO透明导电薄膜为六角纤锌矿结构的多晶薄膜,且具有c轴择优取向。当溅射功率为150W时,薄膜电阻率达到最小值1.66×10–3Ω·cm,在可见光区平均透过率超过93%。