A review of β-Ga_2O_3 single crystal defects, their effects on device performance and their formation mechanism

As a wide-bandgap semiconductor(WBG), β-Ga_2O_3 is expected to be applied to power electronics and solar blind UV photodetectors. In this review, defects in β-Ga_2O_3 single crystals were summarized, including dislocations, voids, twin, and small defects. Their effects on device performance were discussed. Dislocations and their surrounding regions can act as paths for the leakage current of SBD in single crystals. However, not all voids lead to leakage current. There's no strong evidence yet to show small defects affect the electrical properties. Doping impurity was definitely irrelated to the leakage current. Finally, the formation mechanism of the defects was analyzed. Most small defects were induced by mechanical damages. The screw dislocation originated from a subgrain boundary. The edge dislocation lying on a plane slightly tilted towards the(102) plane, the(101) being the possible slip plane. The voids defects like hollow nanopipes, PNPs, NSGs and line-shaped grooves may be caused by the condensation of excess oxygen vacancies, penetration of tiny bubbles or local meltback. The nucleation of twin lamellae occurred at the initial stage of "shoulder part" during the crystal growth. These results are helpful in controlling the occurrence of crystal defects and improving the device performance.

Growth and fundamentals of bulk β-Ga_2O_3 single crystals

The rapid development of bulk β-Ga_2O_3 crystals has attracted much attention to their use as ultra-wide bandgap materials for next-generation power devices owing to its large bandgap(～ 4.9 eV) and large breakdown electric field of about8 MV/cm. Low cost and high quality of large β-Ga_2O_3 single-crystal substrates can be attained by melting growth techniques widely used in the industry. In this paper, we first present an overview of the properties of β-Ga_2O_3 crystals in bulk form. We then describe the various methods for producing bulk β-Ga_2O_3 crystals and their applications. Finally, we will present a future perspective of the research in the area in the area of single crystal growth.

Effect of temperature on photoresponse properties of solar-blind Schottky barrier diode photodetector based on single crystal Ga_2O_3

A solar-blind photodetector is fabricated on single crystal Ga_2O_3 based on vertical structure Schottky barrier diode. A Cu Schottky contact electrode is prepared in a honeycomb porous structure to increase the ultraviolet(UV) transmittance.The quantum efficiency is about 400% at 42 V. The Ga_2O_3 photodetector shows a sharp cutoff wavelength at 259 nm with high solar-blind/visible(= 3213) and solar-blind/UV(= 834) rejection ratio. Time-resolved photoresponse of the photodetector is investigated at 253-nm illumination from room temperature(RT) to 85.8℃. The photodetector maintains a high reversibility and response speed, even at high temperatures.

Effect of Fe_2O_3 on non-isothermal crystallization of CaO-MgO-Al_2O_3-SiO_2 glass

The crystallization behavior and kinetics of CaO-MgO-Al2O3 SiO2（CMAS） glass with the Fe2O3 content ranging from zero to 5%were investigated by differential scanning calorimetry（DSC）.The structure and phase analyses were made by Fourier transform infrared spectroscopy（FT-IR） and X-ray diffraction（XRD）.The experiment results show that the endothermic peak temperature about 760℃ is associated with transition and the exothermic peak temperature about 1000℃ is associated with crystallization.The crystallization peak temperature decreases with increasing the Fe203 content.The crystallization mechanism is changed from two-dimensional crystallization to one-dimensional growth,and the intensity of diopside peaks becomes stronger gradually.There is a saltation for the crystallization temperature with the addition of 0.5%Fe2O3 due to the decomposition of Fe2O3.Si-O-Si,O-Si-O and T-O-T（T=Si,Fe,Al） linkages are observed in Fe2O3-CaO-MgO-Al2O3-SiO2 glass.

Identification and characterization of single crystal Bi_(2)Te_(3-x)Se_(x) alloy

The results of experimental investigation of n-type semiconductor based on Bi2Te3 alloy were presented. This material is used in manufacture of thermoelectric coolers and electrical power generation devices. BizTe2.88Se0.12 solid solution single crystal has been grown using the Czochralski method. Monitoring of structure changes of the sample was carried out by electron microscope. The elemental composition of the studied alloy was obtained by energy dispersive spectrometry （EDS） analysis and empirical formula of the compound was established. X-ray diffraction analysis confirmed that the Bi2Te2.88Se0.12 sample was a single phase with rhombohedral structure. The behavior upon heating was studied using differential thermal analysis （DTA） technique. Changes in physical and chemical properties of materials were measured as a function of increasing temperature by thermogravimetric analysis （TGA）. The lattice parameters values obtained by X-ray powder diffraction analyses of Bi2Te2.88Se0.12 are very similar to BizTe3 lattice constants, indicating that a small portion of tellurium is replaced with selenium. The obtained values for specific electrical and thermal conductivities are in correlation with available literature data. The Vickers microhardness values are in range between HV 187 and HV 39.02 and decrease with load increasing. It is shown that very complex process of infrared thermography can be applied for characterization of thermoelectric elements and modules.

Centimeter-sized Cs_(3)Cu_(2)I_(5)single crystals grown by oleic acid assisted inverse temperature crystallization strategy and their films for high-quality X-ray imaging

Low-dimensional halide perovskites have become the most promising candidates for X-ray imaging,yet the issues of the poor chemical stability of hybrid halide perovskite,the high poisonousness of lead halides and the relatively low detectivity of the lead-free halide perovskites which seriously restrain its commercialization.Here,we developed a solution inverse temperature crystal growth(ITCG)method to bring-up high quality Cs_(3)Cu_(2)I_(5)crystals with large size of centimeter order,in which the oleic acid(OA)is introduced as an antioxidative ligand to inhibit the oxidation of cuprous ions effieiently,as well as to decelerate the crystallization rate remarkalby.Based on these fine crystals,the vapor deposition technique is empolyed to prepare high quality Cs_(3)Cu_(2)I_(5)films for efficient X-ray imaging.Smooth surface morphology,high light yields and short decay time endow the Cs_(3)Cu_(2)I_(5)films with strong radioluminescence,high resolution(12 lp/mm),low detection limits(53 nGyair/s)and desirable stability.Subsequently,the Cs_(3)Cu_(2)I_(5)films have been applied to the practical radiography which exhibit superior X-ray imaging performance.Our work provides a paradigm to fabricate nonpoisonous and chemically stable inorganic halide perovskite for X-ray imaging.

Crystal Growth and Properties of Co^(2+) doped Y_3Sc_2Ga_3O_(12) Single Crystal

Single crystal of cobalt (Co)-doped Y3Sc2Ga3O12 (YSGG) with the dimensions up to Φ20×40 mm3 and undoped YSGG crystal with the dimensions up to Φ28×60 mm3 have been grown using the Czochralski technique. The structure of the crystal was characterized by the X-ray powder diffraction (XRPD) method. The absorbance spectra of the crystal shows that it has strong absorption bands at 606 and 1540 nm. The results indicate that the crystal Y3Sc2Ga3O12 may be a kind of good Q-switch material.

Co and Ni single sites on the(111)n surface ofγ-Al2O3–a periodic boundary DFT study

The influences of increasing the number of d-electrons in the single metal(Fe-like)substituted(111)n surface ofγ-Al2O3 on its possible catalytic effects were explored.The energetic properties,local structures,and in-site electron configurations of the most active tri-coordinated Co and Ni single-site(111)n surface ofγ-Al2O3 have been studied using the density functional theory(DFT)approach under periodic boundary conditions.The replacement of Al by a Co or Ni atom on the I position of the(111)n surface leads to significant elongations of metal–O distances.The energy released from the substitution process on the AlI site of the(111)n surface follows the sequence NiI(164.85 kcal mol−1)>CoI(113.17 kcal mol−1)>FeI(44.30 kcal mol−1).The triplet and quintet(ground state)of the CoI substituted complex are energy degenerate.Also,the doublet and quartet(ground state)of the NiI substituted complex have the same stable energy.This energy degeneracy comes from theα–βelectron flipping on the p-orbital of the neighboring O that is next to the substituted CoI or NiI site on the(111)n surface ofγ-Al2O3.Different from the FeI substituted single-site(111)n surface,in which the electron configuration of FeI varies according to its spin-multiplicity state,substituted NiI has a unique d8 electron configuration in all three spin states,and similarly,CoI has a unique d7 electron configuration in all three open shell spin states.An increase of the population of d-electrons in the single metal substituted(111)n surface ofγ-Al2O3 is likely to provide a more stable electron configuration in the metal catalytic center.

Synthesis of YAG∶Ce^(3+) Phosphor by Polyacrylamide Gel Method and Promoting Action of α-Al_2O_3 Seed Crystal on Phase Formation

YAG： Ce^3 ＋ phosphor particles were prepared using polyacrylamide gel method. The structure evolution of powders during annealing process was followed by X-ray diffraction determination. It is found that some intermediate phases, including θ-Al2O3, YAM and YAP, are formed when calcining polyacrylamide gel, however, the pure YAG phase can be formed directly when calcining polyacrylamide gel with α-Al2O3 as seed crystal. These facts show that the existence of α- Al2O3 seed crystal can block the formation of θ-Al2O3, YAM and YAP, and accelerate its reaction with Y2O3 to form YAG phase directly at lower temperature. The emission peak of prepared YAG ： Ce^3 ＋ phosphor is wide with maximum at 550 nm and the exitation band has two peaks, the major one is around at 460 nm, which matches the blue emission of GaN LED and is suitable for the assemble of white LED. Some fluxes can enhance the photoluminescence intensity of phosphor particles, that can be attributed both to the improvement of crystallization processes of YAG and to the stabilization of trivalence cerium ion in YAG：Ce^3 ＋.

Synthesis of nanocrystalline γ-Al_2O_3 by sol-gel and precipitation methods for methanol dehydration to dimethyl ether

The capability of sol-gel and conventional precipitation techniques for the synthesis of nanocrystalline γ-alumina was investigated. These catalysts were used for vapor-phase dehydration of methanol to dimethyl ether in a fixed-bed reactor under the same operating conditions （T = 300 ？C, P = 1 bar, LHSV = 2.8, 11.7, 26.1 h？1） and characterized by means of N2 adsorption-desorption, NH3-TPD, XRD, TGA and SEM techniques. According to the experimental results, the catalysts prepared using sol-gel method in non-aqueous medium showed better performance compared with those prepared by other methods.

Density functional theory calculations on single atomic catalysis:Ti-decorated Ti3C2O2 monolayer(MXene)for HCHO oxidation

Formaldehyde(HCHO) is a common indoor pollutant, long-term exposure to HCHO may harm human health. Its efficient removal at mild conditions is still challenging. The catalytic oxidation of HCHO molecules on a single atomic catalyst, Ti-decorated Ti3C2O2(Ti/Ti3C2O2) monolayer, is investigated by performing the first principles calculations in this work. It demonstrates that Ti atoms can be easily well dispersed at the form of single atom on Ti3C2O2 monolayer without aggregation. For HCHO catalytic oxidation, both Langmuir-Hinshelwood(LH) and Eley-Rideal(ER) mechanisms are considered. The results show that the step of HCHO dissociative adsorption on Ti/Ti3C2O2 with activated O2 can release high energy of 4.05 e V based on the ER mechanism, which can help to overcome the energy barrier(1.04 e V) of the subsequent reaction steps. The charge transfer from *OH group to CO molecule(dissociated from HCHO) not only promotes *OH group activation but also plays an important role in the H2 O generation along the ER mechanism. Therefore, HCHO can be oxidized easily on Ti/Ti3C2O2 monolayer, this work could provide significant guidance to develop effective non-noble metal catalysts for HCHO oxidation and broaden the applications of MXene-based materials.

Infrared active phonon modes and ionicity of single crystal MgAl2O4

Near-normal incident infrared reflectivity spectra of （100） MgAl2O4 spinel single crystal have been measured at different temperatures in the frequency region between 50 and 6000 cm^-1. Eight infrared-active phonon modes are identified, which are fitted with the factorized form of the dielectric function. The dielectric property and optical conductivity of the MgAl2O4 crystal are analysed. From TO/LO splitting, the effective Szigeti charges and Born effective charges at different temperatures are calculated for studying the ionicity and the effect of polarization. Based on the relationship between the （LO-TO）1 splitting, which represents the transverse and longitudinal frequencies splitting of the highest energy phonon band in the reflectivity spectrum, and the ionic-covalent parameter, the four main phonon modes are assigned. MgA1204 can be considered as a pure ionic crystal and its optical characters do not change with decreasing temperature, so it may be used as a suitable substrate for high-Tc superconducting thin films.

Effect of Rare Earth on the Crystallization Behavior of Li_2O-Al_2O_3-SiO_2 Glass-ceramic

X-ray powder diffraction and Fourier transform infrared spectroscopy were applied for characterization of Li2O-Al2O3-SiO2 glass-ceramic powders doped with Eu2O3,Gd2O3 and Er2O3,respectively,in the conditions of different heat-treatment temperatures and with various amounts.The powders were derived from the polyacrylamide gel method.The results show that,the wet gels prepared by polyacrylamide perform a unique crystallization behavior in the process of drying,comparing with some customary preparation such as melt processing.The main crystal phase and crystallization sequence of Li2O-Al2O3-SiO2 micro-powders have no distinct with addition of Eu2O3,Gd2O3 or Er2O3,while the crystallization temperature of the β-spodumene decreased and the amount of the β-spodumene increased.

CuO/γ-Al_2O_3和CuO-CeO_2-Na_2O/γ-Al_2O_3催化吸附剂的脱硝性能

利用改进的溶胶凝胶法制备CuO／γ-Al2O3和CuO-CeO2-Na2o／γ-Al2O3催化吸附剂颗粒，在固定床上测试其催化脱硝活性。2类催化吸附剂250-400℃范围内脱硝效率稳定在70％以上。在350℃时效率稳定在最高值。利用程序升温方法研究了2类催化剂对NH3和NO的氧化性能，发现NH3在高于400℃下急剧氧化生成N2、NO和N2O，是脱硝效率下降的主要原因。CuO／γ-Al2O3催化剂能将NO氧化生成N02，NO在催化剂上的吸附对脱硝过程有重要作用。改进的CuO-CeO2-Na2o／γ-Al2O3催化剂能使NH3在高温400℃下不被氧化，也促进了NO在催化剂表面的吸附，从而提高了催化剂脱硝效率。催化反应的机理为NO吸附在催化剂表面，氧化生成吸附态的NO2，再与吸附催化剂上的NH3反应。

α-Al_2O_3的晶体结构与价电子结构

对α Al2 O3 的晶体结构进行了详细的讨论 ,通过各种立体插图 ,对比分析了α Al2 O3 的菱面体晶胞和六方晶胞 ,并对每种晶胞中各种原子的排列位置进行了深入分析 ,确定了某一具体位置的O2 -或Al3 + 与其它离子之间的主要键距 ,最后根据“固体与分子经验电子理论 (EET)”计算出了α Al2 O3 晶体的价电子结构 ,并以图示的方式把主要的键及键距标示在图中 ,使能直观地看到α Al2 O3 晶体中最强键及次强键等在晶体中的方位 ,便于分析α Al2 O3 的结构与性能的相互关系。

TiO_2和α-Al_2O_3晶体的生长习性

通过水热法制备粉体的实验观察到金红石、锐钛矿和а－Ａｌ２Ｏ３晶体的生长习性．采用配位多面体生长习性法则合理地解释了ＴｉＯ２和а－Ａｌ２Ｏ３的生长习性．其主要结果为а－Ａｌ２Ｏ３晶体的生长习性为平板｛０００１｝，其各晶面的生长速度为：Ｖ｛０００１｝＜Ｖ｛１１２３｝＜Ｖ｛０１１２｝＝Ｖ｛１１２０｝＜Ｖ｛０１１０｝。金红石的生长习性为柱状，其各晶面的生长速度为：Ｖ＜１１０＞＜Ｖ＜１００＞＜ Ｖ＜１０１＞＜ Ｖ＜００１＞＜ Ｖ＜１１１＞；锐钛矿的生长习性为四面体，其各晶面的生长速度为Ｋ＜０１０＞＝Ｖ＜００１＞＞Ｖ＜０１０＞＞Ｖ＜１１１＞．而ＰＢＣ理论很难合理地解释а－Ａｌ２Ｏ３晶体的生长习性．

钡改性的Ni/γ-Al_2O_3催化剂用于甲烷部分氧化的研究

800℃、80 000h-1、CH4/O2/N2=14/7/79下比较了质量分数20%的N i/-γA l2O3和Ba改性的N i/-γA l2O3催化剂,用于甲烷部分氧化反应的活性和选择性。结果表明,Ba的添加提高了镍基催化剂的活性和稳定性。BET和XRD表明,Ba的加入有利于高温焙烧下抑制大颗粒的N iA l2O4的形成,保持了高比例的活性镍组分,提高了催化剂催化活性。常压下,xCH4接近100%,sCO、sH2达到92.2%和98.1%,催化剂15h内活性稍微下降。Ba的加入使A l2O3的晶型转化温度由800℃提高到900℃,提高了载体的稳定性。

二苯并噻吩和4-甲基二苯并噻吩在Mo和CoMo/γ-Al_2O_3催化剂上加氢脱硫的反应机理

研究了二苯并噻吩(DBT)和4-甲基二苯并噻吩(4-MDBT)在Mo/γ-Al_2O3和CoMo/γ-Al_2O_3上加氢脱硫反应的产物分布及其可能的反应网络,并通过反应压力和温度对产物分布的影响,揭示了加氢脱硫反应的可能机理。DBT在Mo/γ-Al_2O_3上的加氢脱硫反应主要通过直接氢解路径和加氢路径进行,两种途径的作用相近;在CoMo/γ-Al_2O_3催化剂上的加氢脱硫主要通过直接氢解路径进行。4-MDBT在Mo/γ-Al_2O_3和CoMo/γ-Al_2O_3上的加氢脱硫反应主要通过加氢路径进行。Co的加入有助于提高Mo/γ-Al_2O_3催化剂的加氢脱硫活性,尤其是直接氢解脱硫活性。4-MDBT加氢脱硫反应中加氢路径的相对作用显著大于DBT加氢脱硫反应的加氢路径,间接证明4-MDBT的加氢脱硫过程存在对“端连吸附”的空间位阻。4-MDBT分子中甲基的供电子作用有利于促进苯环的加氢反应,从而有助于缩小与DBT分子间加氢脱硫活性的差别。在DBT和4-MDBT加氢脱硫反应中,反应压力和温度对加氢路径的影响大于对氢解路径的影响。

Ni^(2+)在γ-Al_2O_3上的分散状态及负载型Ni/γ-Al_2O_3催化剂的α-蒎烯加氢活性(英文)

用X-射线衍射(XRD)、紫外-可见漫散射光谱(UV-VisDRS)、程序升温还原(TPR)、CO化学吸附和微反测试等方法研究了Ni2+在γ-Al2O3上的分散状态和负载型Ni/γ-Al2O3催化剂的α-蒎烯加氢催化活性。结果表明,当Ni2+负载量远低于其在γ-Al2O3载体表面分散容量时,Ni2+优先嵌入载体表面四面体空位,随着Ni2+负载量的增加,嵌入载体表面八面体空位Ni2+的比例增大。由于八面体Ni2+易被还原为金属态Ni0,NiO/γ-Al2O3样品的还原度随Ni2+负载量的增加而大幅度地增加,经氢还原所得Ni/γ-Al2O3催化剂的CO吸附量和α-蒎烯加氢催化活性大幅度增加。对La2O3助剂的作用进行了研究,结果表明分散在γ-Al2O3上的La3+物种可阻止Ni2+嵌入γ-Al2O3表面四面体空位,增大了八面体Ni2+物种所占比例,提高了催化剂的还原度,故Ni-La2O3/γ-Al2O3催化剂催化活性高于Ni/γ-Al2O3催化剂。

焙烧温度对CuO/γ-Al_2O_3和CeO_2-CuO/γ-Al_2O_3催化剂NO还原活性的影响

用浸渍法制备了CuO γ Al2O3催化剂和CeO2改性的CeO2 CuO γ Al2O3催化剂,考察了焙烧温度对CuO γ Al2O3和CeO2 CuO γ Al2O3催化剂C3H6还原NO反应活性的影响,以及CeO2的添加量对CeO2 CuO γ Al2O3催化剂C3H6还原NO反应活性的影响。结果表明,在200℃～500℃的焙烧温度范围内,焙烧温度对CuO γ Al2O3催化剂的活性影响很小;在500℃～800℃的焙烧温度范围内,随着焙烧温度的升高CuO γ Al2O3催化剂的活性急剧下降,由XRD物相测定结果可知,归因于对反应表现惰性的尖晶石CuAl2O4相的生成。当焙烧温度为500℃时,CeO2的添加对CuO γ Al2O3催化剂的活性影响很小;当焙烧温度为800℃时,CeO2的添加对CuO γ Al2O3催化剂有明显的助催化作用,当Ce和Cu的摩尔比为1∶10时,NO转化率较为理想。