液封坩埚下降法生长非掺杂InP单晶的特性研究

用液封坩埚下降(LE-VB)法沿〈100〉晶向成功地生长了非掺杂InP单晶。LE-VB晶体的4.2K光致发光谱包含束缚于中性浅受主上的激子发光、与Zn受主相关的施主-受主(DA)对发光及其声子伴线、以及与本征缺陷等有关的深能级发光三部分。通过与液封直拉(LEC)生长的籽晶的光致发光谱比较表明,在LE-VB晶体中,束缚于中性浅受主上的激子发光与籽晶中的相差不大;DA对发光的晶格弛豫比籽晶中的小;与本征缺陷等有关的深能级发光强度比籽晶中的弱。晶体的室温光致发光谱仅包含带-带发光,其发光强度形貌测试结果表明,LE-VB晶体的带-带发光强度比LEC籽晶的强。用Huber法对晶片腐蚀的结果表明,在LE-BV晶体中,位错密度仅为LEC籽晶中的三分之一。分析认为,在LE-VB晶体中,本征缺陷和位错等浓度较低,可能是其带-带发光强度比在LEC籽晶中强的物理起因。     

黄-里斯因子及其在阐释固体有关光学性质的关键作用

1950年黄昆先生与A.Rhys(里斯,黄昆先生夫人,中文名李爱扶)发表了F-中心的光吸收与非辐射跃迁理论的论文,这一论文被公认为是处理电子-声子互作用在固体缺陷光吸收的先驱开创性量子理论工作,其中首先由黄昆先生所推导和明确的一个用于表征电子-声子耦合强度的无量纲因子,被广泛采用和推崇为黄-里斯因子(Huang-Rhys factor),也被简称为S因子.本文试图总结黄-里斯因子的物理内涵,以及它在阐释几种固体有关光学性质中的关键作用,包括在深缺陷中心发光以及带边浅杂质束缚激子发光中的支配作用.研究发现,在不同性质的固体材料中,电子(激子)-声子耦合强度可以分为极弱耦合(黄-里斯因子远远小于1)、中等耦合(黄-里斯因子在1—5之间)以及强耦合(黄-里斯因子远远大于1)等几种情况.限于篇幅及个人理解,本文仅讨论GaN各种带边激子、二维单原子层半导体激子、无机卤族钙钛矿纳米晶片激子以及金刚石单晶中NV复合中心等极弱及中等强度耦合等几种情况,以纪念黄昆先生诞辰百周年.     

在正向电压激发下ZnSe MIS二极管的自由激子发光

研究了最低温度为20~30K时,在正向电压激发下ZnSe MIS二极管的激子发光光谱,在这一温度下,二极管有可能通过足以产生发光的电流.对于利用通常气相技术生长的高纯晶体所制备的二极管,其电致发光几乎完全由Γ8→Γ6自由激子发光的1LO和2LO声子伴线所组成.根据Gross等人的半经典理论,讨论了两个谱带的形状.结果是谱带的宽度和不对称性归结为激子服从Maxwell-Boltzmann分布,其有效激子温度接近于晶格温度.     

不同激发密度下CdS晶体的光致发光和受激发射

本文主要研究在77-111K温度范围内、不同激发密度的N2激光器的337.1nm谱线激发下,激子-激子(Ex-Ex)、激子-载流子(Ex-e)的相互作用和发射一个LO声子(Ex-1LO)、两个LO声子(Ex-2LO)的自由激子的辐射复合行为.并在77K温度下观测到由Ex-Ex发射产生的受激发射.     

高纯汽相生长GaP的场致发光及电学性质

研究了以汽相外延法在整片单晶GaP衬底上生长的高纯GaP的场致发光、霍尔系数、电阻率同温度的关系。在77°K和300°K分别获得高达2370厘米~2/伏秒和189厘米~2/伏秒的霍尔迁移率。以Zn 扩散制成的二极管的场致发光表现为本征复合。在77°K时,除了由于在中性施主位置上的束缚激子复合而引起的狭的非声子谱线外,近边带场致发光还呈现出一组界线分明的谱峰,相应于自由激子的声子协助的复合(下文中简称为“声协”复合)。这些观察到的峰,既和 TA、LA、TO声子的吸收有关,也和它们的发射有关;它们的能量分别为12.5,31.0,44.0毫电子伏。和声子发射有关的谱峰强度对于TO、LA和TA声子来说,大概比率是1:3:1.5。这些能量和相对强度是和本征GaP的吸收及阴极射线发光数据一致。在氮和别的任意杂质浓度很低的器件中,场致发光和温度的关系表明:300°K的发射以本征复合占优势。     

CdSe/CdZnSe超晶格的激子光学性质的研究

用分子束外延法在GaAs衬底上生长了CdSe/Cd0.65Zn0.35Se超晶格结构。利用X射线衍射（XRD）、77K下变密度激发的光致发光光谱和变温度光致发光光谱研究了CdSe/CdZnSe超晶格结构和激光复合特性，在该材料中观测到激子－激子散射发射峰，变密度激发光致发光光谱和谱温度光致发光光谱证实了这一现象，激子发射峰的线宽随着温度的升高而展宽，低温时发光峰的宽度主要是由合金组分和阱垒起伏引起的，没温时激子线宽展宽是由于激子与纵光学声子和离化的施主杂质间的散射作用引起的，光致发光的强度随着温度的升高而降低，这主要是由激子的热离化造成的，也就是说，热激发使得电子或空穴由阱中跃迁至垒上。     

GaPN混晶的瞬态发光特性

通过对GaP1-xNx混晶的瞬态发光特性的研究,揭示了在低组分下N杂质从NNi对束缚激子的特性逐渐向高组分下形成GaP1-xNx混晶的杂质带的演变。在较低组分下,样品的发光由NNi对束缚激子及其声子伴线构成,从NN1到NN4的衰减时间分别在90～30ns变化。当组分提高到x～1．3％以上时,样品的发光呈现出一个宽带,并按单指数规律衰减,辐射复合寿命大约在数十个纳秒量级,且随着N组分的增加,寿命相对减小;但在最高组分(x～3．1％)时,其寿命仍与NN4束缚激子的寿命相当(～30ns),说明GaP1-xNx混晶新形成的杂质带仍然保持束缚激子较长的辐射复合寿命。且该杂质带低能端载流子的寿命比高能端载流子的寿命长,导致了其时间分辨谱向低能端的移动。同时在低组分样品的时间分辨谱的测量中,直接观察到了从较浅NN对束缚激子向较深NN对束缚激子的能量传输现象。     

GaP:(Bi,N)晶体中束缚激子的辐射复合及能量转移

本文研究了在4.2K—147K温度范围内GaP:(Bi,N)晶体的光致发光光谱的精细结构,积分强度及其随温度的变化,并将它们与GaP:Bi,GaP:N光谱进行比较。首次发现在GaP:(Bi,N)晶体中激发能量从孤立N中心和NNi对(i≥3)中心到Bi中心的转移,增大了Bi束缚激子态的浓度,使Bi发射带增强。     

正向电压激发下CdS MIS发光二极管中的自由激子发光

在44~77K温度范围内.在正向电压激发下的Cds MIS二极管中,观测到了发射0、1或2个纵光学(O、1LO或2LO)声子的自由激子的辐射衰减.根据激子的动能分布,讨论了1LO和2LO声子协助的伴线的形状和温度依赖.这里激子的有效温度等于晶格温度.     

GaP1-xNx混晶中新束缚态的研究

利用变温光致发光(PL)谱及时间衰退发光谱研究了一系列CaP1-xNx混晶的光学性质。GaP1-xNx混晶的PL谱从低组分的NN对束缚激子及其声子伴线到高组分杂质带发光的特征,表现出明显的带隙降低的趋势。测量结果显示,在组分x≥0．24％的样品的发光谱中NN1能量之下已经开始出现几个新的束缚态,对其激活能的拟合及对时间衰退发光谱的分析表明,新的束缚态一方面仍保留有N束缚激子的性质,另一方面又表现出有别于NN对束缚激子的发光机制。说明新的束缚态有可能由新的N原子组成(如NNN原子)或与NN对束缚激子存在着某种相互作用。     

老化产生的深能级对GaP纯绿发光二极管发光效率的影响

测量了GaP纯绿发光二极管老化前后的可见和近红外发光光谱,研究了老化产生的深能级的来源及其对二极管发光效率的影响.在老化后的发光光谱中观测到650nm和1260nm发光带,发现1260nm发光带的发光强度随老化时间的增加而增强.实验结果表明老化产生的与磷相关的深能级严重地影响了GaP纯绿LED的发光效率.     

GaP纯绿发光二极管的近红外发光研究

本文测量了GaP纯绿发光二极管在室温和液氮温度下的近红外发光光谱,观测到许多重叠的宽带发光.按高斯线型对光谱进行拟合,将其分解为6个发光谱峰,讨论了这些深能级发光的来源和它们对GaP发光二极管的发光强度的影响.     

The optical properties of Be,Mg and Zn-diffused gallium phosphide

Interest in the Ga-site acceptors Be and Mg was stimulated by the possibility that they might produce efficient luminescence on association with O, analogous to the well-known red Zn-O luminescence in GaP but at higher transition energy. Attention was directed to diffusion doping by Be and Mg of GaP O-doped during growth because the reactivity of Be and Mg with O renders double doping during crystal growth very difficult. Structured green donor-acceptor pair spectra were observed at 1.6°K from many Be-diffused crystals, yielding an accurate measure of (E_A)_BE, 50 ± 1 meV. Moderately efficient orange-red luminescence was also observed below ∼ 100 °K from these crystals, but the intensity of this luminescence decreased rapidly to negligible levels by ∼ 200°K. This luminescence also contains sharp structure at 1.6°K, of a form characteristic of the decay of excitons bound to complex centres. Many sharp phonon replicas occur, involving local modes as well as characteristic GaP modes. One set of no-phonon lines, at least, near 2.19 eV, shows zero-field splitting, luminescence decay times and behaviour in magnetic and external strain fields characteristic of exciton decay at a centre with <100>; or <111>-type symmetry axes, containing no extra electronic particles. The exciton state is split by 2.4 meV by J-J coupling, and the axial field of the centre splits the hole states by ∼ 1.0 meV. These bound excitons are specifically characteristics of diffused GaP and appear analogous to bound excitons observed below 2.12 eV in Zn-diffused GaP. It is probable that the relevant centres contain diffusion components such as Be or Zn interstitials and improbable that O_P is involved. By contrast, weak orange bound exciton luminescence observed in Mg-diffused GaP does involve O, presumably as O_P. No analysis of the magneto-optical behaviour of this Mg-related bound exciton was possible in our crystals, so its symmetry axis was not established. It is possible that this is the Mg_Ga-O_P bound exciton. If so, the two-fold reductions in the exciton localisation energy from ∼ 0.32 eV to ∼ 0.15 eV and in the mass of the Ga-site substituent has produced dramatic changes in the form of the phonon cooperation between the Zn-O and “Mg-O” excitons. The “Mg-O” exciton luminescence is not dominant in our crystals, even at low temperature. The exciton state is again split by a local crystal field as well as by J-J coupling, but here the former splitting is predominant; 2_∈0 = 3.9 meV, Δ = 0.60 meV.     

Interaction of excitons in indirect solid solutions of In1−xGaxP at high levels of excitation

The cathode luminescence spectra of GaP and solid solutions of In_1–xGa_xP (with an indirect energy band structure) obtained by liquid-phase epitaxy are investigated at T=77 and 9°K. It is established that the recombination of excitons on neutral donors and the pure exciton recombination with the participation of TA (=13±1 meV), LA (=31±1 meV), and TO (=43±2 meV) phonons. dominate in the low-temperature luminescence spectra of GaP and In_1–xGa_xP with a small concentration of photon impurities. The complex luminescence band that arises for sufficiently high levels of excitation and at T = 9°K is attributed to the luminescence of an electron-hole drop (EHD). The transformation of spectral form of the EHD band with the transition from GaP to In_1–xGa_xP is attributed to a simultaneous reduction in the contribution of the TA and TO replicas and to the appearance of a phononless component in the luminescence of the EHD.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 37–40, September, 1985.     

Three-photon non-linear cross-section of gallium phosphide

The luminescence of GaP which follows non-linear optical excitation has been studied by using three- and two-photon optical pumping by a neodymium and a ruby laser, respectively. By comparing the intensities of the excitonic A-line emission in the two spectra, the three-photon cross section is obtained. This result is compared with previous experimental and theoretical values.     

Luminescence of Pr,Nd and Yb ions implanted in GaAs and GaP

New experimental data on luminescence spectra of Pr and Nd ions implanted into GaAs and GaP crystals and the results on luminescence kinetics of Nd doped GaP are presented. The results show that RE ions form different complexes in measured samples.     

Fabrication and characterization of GaP/polymer nanocomposites for advanced light emissive device structures

GaP nanoparticles have been prepared using white P and a mild aqueous synthesis at decreased temperature followed by ultrasonication and stored as the suspension in water–ethanol mixture. They were characterized by standard methods of X-ray diffraction, transmission electron microscopy, Raman light scattering, and photoluminescence. Properties of GaP nanoparticles were compared with industrial and specially grown perfect GaP single crystals. It was shown that the GaP nanoparticles in suspension are the most suitable for high quality GaP/polymers nanocomposites because only they are uniform with dimensions of about 10 nm which is optimal for appearance of the pronounced quantum confinement effect. Polyglycidyl methacrylate (PGMA), polyglycidyl methacrylate-co-polyoligoethyleneglycol methacrylate (PGMA-co-POEGMA), and biphenyl vinyl ether (BPVE) polymers were used to prepare GaP polymer nanocomposites. The thickness of the polymer nanocomposite film was about 250–300 nm defined from AFM scratch experiment. The resulting nanocomposites yielded a bright luminescence at room temperature in a broad band with the maximum ranging from 2.5 to 3.2 eV and showed pronounced quantum confinement effects and other interesting and important for application phenomena leading to dramatic 1 eV expansion of GaP luminescence to the UV spectral region.     

Decay of the red Cu-S pair luminescence in GaP

The red Cu-S pair luminescence in GaP has been studied by time resolved spectroscopy at several photon energies between 1.39 and 1.77 eV for times shorter than 40 μs. Superimposed on a long lasting luminescence a fast decay was observed showing the typical behaviour of donor-acceptor (DA) pair recombination. The transition probability W_m was estimated to be 10⁶ s^-1, being of the same order of magnitude as that of the other known DA pairs in GaP.     

Luminescence of Molecules with Internal Charge Transfer upon Longwave Excitation

We have studied the spectral properties of luminescence of laurdan molecules in glycerin upon excitation at the red edge of the absorption band at different temperatures. The most significant red-wave shift of the spectra (10 nm) for the longwave band of dual fluorescence is observed depending on the excitation wavelength at a low temperature of 260 K when a solvent forms a fairly rigid matrix. At the same time, at increased temperatures of up to 370 K a small bathochromic shift and a change in the shape of the luminescence bands are also recorded reliably. Changes in the excitation spectra were observed when luminescence was recorded in the bands of the LE- and CT states. The difference spectrum responsible for the additional absorption that does not make a contribution to the longwave luminescence component has been isolated. The decay kinetics of both luminescence components have been measured and their expansions in decay constants have been analyzed. The experimental dependences obtained point to the complex mechanism of inhomogeneous broadening of spectra.