A stoichiometric mixture of evaporating materials for ZnAl2Se4 single-crystal thin films was prepared in a horizontalelectric furnace. These ZnAl2Se4 polycrystals had a defect chalcopyrite structure, and its lattice constants were a0=5.5563Åand c0=10.8897Å.To obtain a single-crystal thin film, mixed ZnAl2Se4 crystal was deposited on the thoroughly etched semi-insulating GaAs(100) substrate by a hot wall epitaxy (HWE) system. The source and the substrate temperatures were 620oCand 400oC, respectively. The crystalline structure of the single-crystal thin film was investigated by using a double crystal X-ray rocking curve and X-ray diffraction ω-2θ scans. The carrier density and mobility of the ZnAl2Se4 single-crystal thin filmwere 8.23×1016cm−3 and 287m2/vs at 293K, respectively. To identify the band gap energy, the optical absorption spectra ofthe ZnAl2Se4 single-crystal thin film was investigated in the temperature region of 10-293K. The temperature dependence ofthe direct optical energy gap is well presented by Varshni's relation: Eg(T)=Eg(0)−(αT2/T+β). The constants of Varshni'sequation had the values of Eg(0)=3.5269eV, α=2.03×10−3eV/K and β=501.9K for the ZnAl2Se4 single-crystal thin film.The crystal field and the spin-orbit splitting energies for the valence band of the ZnAl2Se4 were estimated to be 109.5meVand 124.6meV, respectively, by means of the photocurrent spectra and the Hopfield quasicubic model. These results indicatethat splitting of the ∆so definitely exists in the Γ5 states of the valence band of the ZnAl2Se4/GaAs epilayer. The threephotocurrent peaks observed at 10K are ascribed to the A1-, B1-exciton for n=1 and C21-exciton peaks for n=21.

Single crystal ZnIn2S4 layers were grown on thoroughly etched semi-insulating GaAs(100) substrateat 450oC with hot wall epitaxy (HWE) system by evaporating ZnIn2S4 source at 610oC. The crystalline structureof the single crystal thin films was investigated by the photoluminescence (PL) and double crystal X-ray rockingcurve (DCRC). The temperature dependence of the energy band gap of the ZnIn2S4 obtained from theabsorption spectra was well described by the Varshni’s relation, Eg(T)=2.9514eV-(7.24×10−4eV/K)T2/(T＋489K). After the as-grown ZnIn2S4 single crystal thin films were annealed in Zn-, S-, and In-atmospheres, theorigin of point defects of ZnIn2S4 single crystal thin films has been investigated by the photoluminescence (PL)at 10K. The native defects of VZn, VS, Znint, and Sint obtained by PL measurements were classified as a donorsor acceptors type. And we concluded that the heat-treatment in the S-atmosphere converted ZnIn2S4 singlecrystal thin films to an optical p-type. Also, we confirmed that In in ZnIn2S4/GaAs did not form the nativedefects because In in ZnIn2S4 single crystal thin films existed in the form of stable bonds.

ZnS 박막을 Hot W긴 법에 의해 증발관 온도, 기판온도 및 외부로부터 유황(5)의 공급을 변수로 하여 제작하여 광학적, 결정 구조적 특성을 분석 ·검토하였다 박막의 증착속도는 증발관 온도 및 5 증기압을 높일수록 증가하였으나 기관온도를 높이면 급격히 감소하였다. 박막의 광학적 특성은 증착속도와 밀접하게 관계하고 있다고 사료되며, 실온에서의 금지대 폭은 이론 값보다 작은 3.46∼3.72ev를 나타내어 결정 중에 결함이 존재함을 알 수 있었다. 박막의 구조를 분석한 결과 어느 경우에 있어서나 섬아연광 구조의 (111) 주 배향성을 나타내었으나 회절피크의 강도 및 반치폭으로부터 결정성은 대체로 양호하지 못했음을 알았다. 그러나, 기판온도 또는 5 공급 등의 제작조건에 따라 광학적, 결정적 특성이 개선되었다.

A new technique to grow a manganese-doped zinc-sulfide(ZnS：Mn) has been proposed using the repeated deposition of the Hot Wall method. The optical characteristics and crystallinity for the ZnS and ZnS：Mn thin films deposited on a quartz glass substrate by the method were investigated. Also, The ZnS：Mn thin film elcetroluminescent devices were fabricated by the method to study luminescence characteristics. All films showed (111)-oriented cubic structure. By the repeated deposition, the deposition rates were decreased, and the optical characteristics and crystalline properties were improved, which clarifies that the method is effective to deposit the thin films with good crystallinity Futhermore, the crystallinity was more improved by the doping of Mn. Only one peak emission at around 585nm originating from Mn luminescent center is observed In the photoluminescent and electroluminescent spectra of ZnS：Mn films and the luminance of the ZnS：Mn-based thin film electroluminescent devices was obtained below 60cd/m2 . The optical and crystalline properties, luminescence characteristics are discussed in terms of the effects of the repeated deposition and Mn-doping.