MOCVD生长AlN/GaN化学反应路径的量子化学研究

应用量子化学的密度泛函理论,对MOCVD生长GaN/AlN薄膜的反应路径进行理论计算和分析,特别是针对Ⅲ族TMX(X=Ga,Al)与V族NH3的反应路径与温度的关系进行研究.计算结果表明:当温度T≤473.15 K时,反应自由能△G＜0,TMX与NH3自发生成配位加合物TMX∶ NH3;当T≥573.15 K时,△G＞0,TMX∶ NH3将重新分解为TMX和NH3.在473.15 K≤T≤573.15 K区间,将存在△G=0,即加合反应达到平衡,反应为双向可逆.随着温度的升高,从加合物变为氨基物DMX∶ NH2的反应概率加大.TMX和MMX的直接热解反应均需要高温激活,而DMX变为MMX则较容易发生.当T＞873.15 K时,DMGa变为MMGa的热解反应将自发进行;当T＞1273.15 K时,DMAl变为MMAl的热解反应将自发进行.在自由基CH3参与下,TMX→DMX(X=Ga、Al)的能垒仅为TMX直接热解能垒的一半,约为30 ～ 40 kcal/mol;在自由基H参与下,TMGa和TMAl的热解反应能垒更低,约为16～ 20kcal/mol.因此,自由基H的产生将大大促进TMX的热解.     

自由基对气相化学反应生长GaN的影响研究

结合化学反应动力学模型,对MOCVD反应器中自由基对GaN生长的化学反应路径的影响进行数值模拟研究。通过对比加入自由基前后RDR反应器中Ga浓度变化,来分析自由基对化学反应热解路径的影响。同时改变压强,分析操作参数的变化对自由基活性的影响。研究发现:在不考虑自由基的反应路径,薄膜生长的主要前体为DMG;而考虑自由基的反应路径,主要的生长前体为MMG。自由基的存在加速了DMG向MMG的热解,使得DMG分解为MMG速度远大于TMG分解为DMG的速度,导致衬底上方的MMG浓度高于DMG。而操作压强的变化仅仅对流动边界层产生了影响,对热解路径影响不大。     

双甜菜碱为客体包合物的三维氢键网格的构筑

利用硫脲和双甜菜碱制备了一种新型的包合物 [^-OOCCH₂N⁺(CH₃)₂]₂(CH₂)₃·4(NH₂)₂CS,用X射线单晶衍射方法测定其晶体结构。结果表明,晶体属三斜晶系,P1ˉ空间群, 其中a=0.884 5(2) nm,b=0.936 7(2) nm,c=0.946 4(3) nm,α=91.591(2)°,β=91.591(2)°,γ=91.591(2)°,Z=1,R₁=0.039 9, wR₂=0.100 6(I>2σ(I))。在标题化合物的晶体结构中,硫脲分子通过N-H…S氢键肩并肩相连形成四聚体,客体分子的羧基通过N-H…O氢键连接硫脲四聚体形成氢键层,客体阳离子部分夹在相邻的氢键层中,形成三明治晶体结构。     

加合反应对MOCVD生长GaN化学反应路径的影响

针对分隔进口垂直高速转盘式(RDR)MOCVD反应器生长GaN的气相化学反应路径进行数值模拟研究.分别考虑TMG与一个NH3的加合反应(模型1)和TMG: NH3与第二个NH3的加合反应(模型2)两种情况,通过对比两种情况下衬底表面附近主要反应前体的浓度大小,判断GaN生长的主导反应路径.通过分析模拟结果发现:只考虑TMG与一个NH3的加合反应时,GaN生长主要遵循TMG热解路径;在考虑TMG: NH3与第二个NH3的加合反应时,GaN生长主要遵循加合路径.由此可见,TMG: NH3与第二个NH3的反应对于MOCVD生长GaN的化学反应路径的选择具有很大的影响.     

垂直转盘式MOCVD反应器中GaN化学反应路径的影响研究

对垂直转盘式MOCVD反应器生长GaN的气相化学反应路径进行研究.结合反应动力学模型,分别采用预混合进口但改变反应腔高度,以及采用环形分隔进口,对反应器的温场、流场和浓度场进行CFD数值模拟,由此确定反应器结构参数对化学反应路径的影响.通过观察主要含Ga粒子的浓度分布以及不同反应路径对生长速率的贡献,判断该反应器可能采取何种反应路径.研究发现,RDR反应器的主要反应路径是TMG热解为DMG,DMG为薄膜沉积的主要前体.反应腔高度变化对反应路径影响较小,但生长速率略有增大;当从预混合进口改为环形分隔进口时,生长更倾向于TMG热解路径,同时生长速率增大,但均匀性变差.     

微反应器策略实现γ-CuI的形貌调控

γ-CuI较宽的能带空隙及较高的离子电导率等特点，使其在光能利用和超快闪烁材料领域有着广泛的应用。γ-CuI的形貌往往对其结构性质有重要的影响，精准地调控其形貌有很大的意义。因此，本文采用微反应法，通过控制不同NH₃·H₂O用量、Cu源、管内反应停留时间及合成温度等因素，结合SEM、XRD和FT-IR等测试手段，对不同合成条件下制备得到的γ-CuI的晶型与形貌进行了研究。并对传统液相沉淀法和微反应法制备的γ-CuI进行了比较。结果表明，当NH₃·H₂O使用量(C_NH3·H2O/C_N2H4)为0.4、管内停留时间为10 s、反应温度为20℃的条件下达到90.5%的最高产率。其中，NH₃·H₂O的使用量对形貌的影响最大，当NH₃·H₂O的使用量为0.4时，合成了形貌均一的棒状γ-CuI。...     

MOVPE生长AlN的气相反应机理的密度泛函理论研究

利用量子化学的密度泛函理论,对MOVPE生长AlN的气相反应路径进行理论计算和分析,特别针对氨基物DMAlNH2形成后的多聚反应、多聚物消去甲烷反应、以及温度的影响关系进行研究.通过对不同反应路径的吉布斯自由能和反应能垒的计算,分别从热力学和动力学上确定最可能的末端气相反应前体.研究发现,氨基物通过与NH3的双分子碰撞,很容易越过较低的能垒,形成稳定的Al(NH2)3.在385 K＜T＜616 K,三聚物(DMAlNH2)3消去CH4变成(MMAlNH)3的反应容易发生.在641 K＜T＜1111 K,二聚物(DMAlNH2)2消去CH4变成(MMAlNH)2的反应容易发生.而(MMAlNH)2、(MMAlNH)3继续消去CH4生成(AlN)2、(AlN)3的反应,由于吉布斯自由能差都大于零,而且能垒也很大,故很难发生.因此,在AlN的MOVPE过程中,Al(NH2)3、(MMAlNH)2和(MMAlNH)3是最可能的三种末端气相反应前体,它们将决定AlN的表面反应生长.     

Ti、V、Ni、Mo对CVD金刚石涂层形核影响

基于密度泛函理论,计算分析了CH₃基团在含有过渡金属元素Ti、V、Ni、Mo的孕镶金刚石颗粒硬质合金基底表面的吸附能、Mulliken电荷分布、电荷密度差和态密度(density of states, DOS)等一系列性质,研究Ti、V、Ni、Mo对孕镶金刚石颗粒硬质合金基底化学气相沉积(chemical vapor deposition, CVD)金刚石涂层形核阶段的影响及其作用机理。计算结果表明:与CH₃基团在WC表面及金刚石表面的吸附相比,Ti、V、Ni、Mo与C原子间有较强的弱相互作用,这使得其对CH₃基团有更强的吸附能力(其中Ti>V>Mo>Ni);吸附能力大小与各原子的价电子结构相关,含有Ti元素的表面对CH₃的吸附最稳定;CH₃基团与Ni原子间更易发生电荷的转移形成共价键,Mo有利于促进CH₃基团的脱氢反应;形核阶段适当添加Ti、V、Ni、Mo这几种过渡金属元素将有利于增加形核密度,改善CVD金刚石膜基界面结合强度。     

水热法合成CsxWO3纳米棒及其红外吸收性能

Cs_xWO₃纳米棒因其优异的近红外吸收性能得到研究人员的广泛关注,但目前水热法合成Cs_xWO₃纳米棒存在易形成等轴状纳米颗粒,或合成温度高,需要后续处理等问题。本文以钨酸铵((NH₄)₆ W₇O₂₄·6H₂O)、氯化铯(CsCl)、盐酸(HCl)和油胺(C₁₈H₃₇N)为原料,在220 ℃水热反应24 h合成了直径和长度分别为10~20 nm和100~250 nm的Cs_0.2WO₃纳米棒。研究了溶剂、合成路径以及HCl对Cs_0.2WO₃纳米棒的物相和形貌的影响,探讨了Cs_0.2WO₃纳米棒的形成机理,测试了Cs_0.2WO₃纳米棒的红外吸收性能。结果表明:过少和过量的HCl不利于合成Cs_0.2WO₃,改变HCl和CsCl的加入顺序,降低(NH₄)₆ W₇O₂₄·6H₂O、CsCl和HCl间的反应速率,有助于合成Cs_0.2WO₃纳米棒,且Cs_0.2WO₃纳米棒的红外吸收性能优于等轴状纳米颗粒。     

铅基卤化物钙钛矿太阳电池的模拟研究

多元硫化物Cd_0.5Zn_0.5S和氧化亚铜Cu₂O载流子迁移率较大,且其制作工艺相对于传统的电子传输层和空穴传输层更为简单,因此这两种材料在钙钛矿太阳电池中具有很好的应用潜力。本文利用SCAPS-1D软件对以Cu₂O和Cd_0.5Zn_0.5S为传输层、以铅基卤化物钙钛矿为吸收层的太阳电池进行模拟,主要研究了该器件的材料厚度、掺杂浓度、禁带宽度等因素对太阳电池性能的影响。结果表明:当光吸收层(CH₃NH₃PbI₃)厚度开始增大时电池性能逐渐提高,但是增大到一定厚度时,电池性能下降,光吸收层的最佳厚度为400 nm;当光吸收层的缺陷态密度小于1.0×10¹⁴ cm^-3时,缺陷态密度对电池性能的影响比较小;此外,铅基卤化物钙钛矿的禁带宽度对电池性能有重要影响,最佳禁带宽度为1.5 eV左右。通过模拟,得到了优化后的性能参数为:开路电压为1.010 V,短路电流密度为31.30 mA/cm²,填充因子为80.01%,电池转换效率为25.20%。因此,Cu₂O/CH₃ NH₃PbI₃/Cd_0.5Zn_0.5S钙钛矿太阳电池是一种很有发展潜力的光伏器件。     

High quality GaN grown by MOVPE

Several nitrogen precursors have been used for the growth of GaN in MOVPE, but so far the best results were obtained using NH₃, even though NH₃ does not produce a significant amount of active species at the growing interface. To produce active species from N₂ or NH₃, a remote plasma-enhanced chemical vapour deposition (RPECVD) process has been implemented. In addition, nitrogen metalorganic precursors, triethylamine and t-butylamine, were also used. To accurately control the critical parameters of the MOVPE of GaN, we have implemented a laser reflectometry equipment, which allows a real-time in situ monitoring of the different steps of the growth, i.e. nitridation of the substrate, nucleation, heat treatment, and deposition. Using an appropriate buffer layer, GaN grown on sapphire using NH₃ as nitrogen precursor, shows sharp low temperature photoluminescence lines (4 meV at 9 K), whereas other nitrogen precursors did not lead to comparable electronic quality.     

喷淋式MOCVD反应器中AlN的生长速率和化学反应路径的数值模拟研究

利用数值模拟方法,结合反应动力学和气体输运过程,研究喷淋式MOCVD反应器中AlN的生长速率和气相反应路径与反应前体流量(NH3和H2)、进口温度、压强、腔室高度等参数的关系.研究发现:薄膜生长前体和纳米粒子前体的浓度决定了不同的生长速率和气相反应路径.在低Ⅴ/Ⅲ比(2000)、高H2流量(12 L/min)、高进口温...     

Effect of heat treatment on phase transformation of aluminum nitride ultrafine powder prepared by chemical vapor deposition

Ultrafine aluminum nitride (AlN) powders were obtained by chemical vapor deposition via AlCl₃–NH₃–N₂ system operated at various temperatures and at a same 200 cm³/min flow rate of NH₃ and N₂, respectively. It has been shown that when the reaction temperature of AlCl₃ and NH₃ was above 600°C, then crystalline AlN powder can be formed; whereas, amorphous AlN was obtained with NH₄Cl if reacted in a lower-temperature zone of the reaction chamber. The amorphous AlN powder was heat treated at 1400°C under NH₃ and N₂ atmosphere for 2 h, then the crystalline phases of the obtained powder belong to a single phase of AlN; a mixture of AlN and Al₂O₃ and only AlON, respectively. On the other hand, if crystalline AlN powder is heat treated at 1400°C under N₂ atmosphere for 2 h, the crystalline phases were composed of the major phase of AlN and a minor phase of Al₂O₃. The morphology, particle size and agglomerate size of the AlN powder were strongly dependent on the heat-treatment temperature. The particle size of AlN powder increases from 28.1 to 45.0 nm, as the heat treatment temperature increases from 800 to 1400°C.     

Enhanced two-dimensional growth of MOVPE InN films on sapphire (0 0 0 1) substrates

MOVPE growth of InN on sapphire substrates is compared using two different designs of horizontal reactor. The major difference between the two designs is a variation in the reactant-gas flow-spacing between the substrate and the ceiling of the quartz chamber: 33 mm for the Type A reactor and 14 mm for Type B. Compared with the Type A reactor, the Type B reactor brings about InN films with a larger grain size. This is especially true when InN is grown at 600°C using the Type B reactor, in which case the two-dimensional (2D) growth of InN is found to be extremely enhanced. An investigation of the NH₃/TMIn molar ratio dependence of the surface morphology of grown InN films using the two reactors suggests that the enhanced 2D growth is attributed to the decrease in the effective NH₃/TMIn ratio in the growth atmosphere. Even using the Type A reactor, a film with enhanced 2D growth can be obtained when the NH₃/TMIn ratio is considerably low (1.8×10⁴). The enhanced 2D growth results in a smaller XRC-FWHM (full-width at half maximum of the X-ray rocking curve) (1500 arcsec), than that for a 3D-grown film (5000 arcsec).     

Effect of NH3 on the growth characterization of TiN films at low temperature

Titanium nitride (TiN) films were obtained by the atmospheric pressure chemical vapor deposition method of the TiCl₄–N₂–H₂ system with various flow rates of NH₃ at 600°C. The growth characteristics, morphology and microstructure of the TiN films deposited were analyzed by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Without NH₃ addition, no TiN was deposited at 600°C as shown in the X-ray diffraction curve. However, by adding NH₃ into the TiCl₄–N₂–H₂ system, the crystalline TiN was obtained. The growth rate of TiN films increased with the increase of the NH₃ flow rate. The lattice constant of TiN films decreased with the increase of the NH₃ flow rate. At a low NH₃ flow rate, the TiN (2 2 0) with the highest texture coefficient was found. At a high NH₃ flow rate, the texture coefficient of TiN (2 0 0) increased with the increase of the NH₃ flow rate. In morphology observation, thicker plate-like TiN was obtained when the NH₃ flow rate was increased. When the flow rate of NH₃ was 15 sccm, Moiré fringes were observed in the TiN film as determined by TEM analysis. The intrinsic strain was found in the TiN film as deposited with 60 sccm NH₃.     

MOMBE growth characteristics of antimonide compounds

This paper describes the MOMBE (metalorganic molecular beam epitaxy) growth characteristics of antimonide compounds using TMIn (trimethylindium), TEGa (triethylgallium) and TIBAl (triisobutylaluminium) as group III sources, and As₄, Sb₄, TEAs (triethylarsine) and TESb (triethylstibine) as group V sources. Large differences in the growth characteristics of GaAs and GaSb MOMBE are observed. These are explained, using a theoretical consideration of the growth mechanism, by the difference in the effective surface coverage of excess As and Sb atoms during the growth. The use of TEAs and TESb instead of As₄ and Sb₄ alters the growth rate variation of both GaAs and GaSb with substrate temperature (T_sub), which results from the interaction of alkyl Ga species with the alkyl radicals coming from the thermally cracked TEAs and TESb. The alkyl exchange reaction process is observed in the growth of AlGaSb using TIBAl and TEGa, where the incorporation rate of Al is suppressed by the coexistence of TEGa on the growth surface, in the low T_sub region. This is caused by the formation of an ethyl-Al bond which is stronger than the isobutyl-Al bond. The composition and the growth rate variations of InGaSb with T_sub are similar to those of InGaAs, which are closely related to the MOMBE growth process and are quite different from those of MBE (molecular beam epitaxy) and MOVPE (metalorganic vapor phase epitaxy) growth. In the MOMBE growth of InAsSb and GaAsSb using TEAs and TESb, the composition variation with T_sub is weaker than that of MBE. This is a superior point of MOMBE growth for the composition control. The electrical and optical properties of MOMBE grown films as well as the quantum well structures are also described.     

化学水浴沉积法制备硫化镉薄膜的微结构和性能

采用化学水浴沉积法在不同氨水用量下制备了Cu(In,Ga)Se₂太阳能电池的缓冲层CdS薄膜,根据化学平衡动力学计算出混合溶液中反应粒子的初始浓度、pH值和离子积,利用台阶仪、扫描电子显微镜(SEM)、X射线衍射仪(XRD)、量子效率测试仪(EQE)和IV测试仪对制备样品的薄膜厚度、表面形貌、晶体结构、量子效率和光电转换效率进行了表征和分析。结果表明:提高氨水用量可以抑制同质反应,促进异质反应,使CdS薄膜晶体结构从立方相向六方相转变,晶粒形状从柳絮状向颗粒状转变,晶粒尺寸逐渐增大,粒径分布更加均匀,薄膜表面更加平整,制备电池的EQE、V_oc、J_sc、FF、R_s等电学参数得到优化,光电转换效率从7.64%提高到13.60%。     

MOVPE growth of GaInP/GaAs hetero-bipolar-transistors using CBr4 as carbon dopant source

Carbon doping of GaAs with carbon tetrabromide (CBr₄) in low pressure MOVPE has been investigated and applied to the fabrication of GaInP/GaAs HBTs. Especially the hydrogen incorporation and the associated acceptor passivation has been studied. The hydrogen found in single GaAs:C layers is predominantly incorporated during cooling the sample under AsH₃ after growth, n-Type capping layers can block this H indiffusion and GaAs:C base layers in HBTs show much lower H concentrations than GaAs:C single layers without a cap. A further reduction of acceptor passivation is possible by optimization of the growth procedure. First HBTs processed from layers with a base that was doped using CBr₄ show promising DC and HF performance (β = 45, for 2 × 20 μm² devices).     

Incorporation of phosphorus during gas phase epitaxy

The PH₃ desorption rate can be reduced and the decomposition rate increased, thereby increasing the P incorporation efficiency by replacing TMIn with InCl created by the pyrolysis of DEIn. InCl generated by cracking DEInCl and uncracked PH₃ could be used for CBE growth of InP provided that H on the PH₃ can be used to remove Cl from the InCl. Evidence is presented that this is possible. Evidence is also provided that P is more readily incorporated during OMVPE growth using TBP than PH₃ because PH₂ is a primary pyrolysis product, and it is less likely to desorb and more likely to decompose than PH₃.