發(fā)布時間：2018-03-14 09:18

  本文選題：花形　切入點：氧化鋅　出處：《中國海洋大學(xué)》2011年碩士論文　論文類型：學(xué)位論文

【摘要】：ZnO是一種重要的II-IV族直接寬禁帶半導(dǎo)體材料,室溫下禁帶寬度為3.37 eV,激子束縛能高達(dá)60 meV,被認(rèn)為是一種有廣闊應(yīng)用前景的紫外光發(fā)射材料。同時它也是一種多功能氧化物材料,在光電、鐵電、壓電、熱電、鐵磁等領(lǐng)域具有優(yōu)異的特性,可廣泛應(yīng)用于透明電極、壓電材料、壓敏電阻、聲波器件和太陽能電池等諸多領(lǐng)域。 目前,ZnO的研究主要集中在ZnO薄膜、ZnO摻雜及ZnO納米結(jié)構(gòu)的研究。在納米結(jié)構(gòu)領(lǐng)域,科研人員已經(jīng)取得了很大進(jìn)展,但納米ZnO器件的應(yīng)用仍然任重而道遠(yuǎn)。眾所周知,材料的性能取決于材料的結(jié)構(gòu),而材料的結(jié)構(gòu)又很大程度上取決于制備方法和工藝。因此,對于材料的形貌、尺寸等的可控制備研究,對于納米ZnO器件的應(yīng)用是至關(guān)重要的前提。 本論文采用簡單的水浴法,以硝酸鋅(Zn(NO_3)_2·6H_2O)、六亞甲基四胺((CH_2)6N_4)和乙二胺(C2H8N2)為原料,制備了微納米花形ZnO結(jié)構(gòu),為研究其生長過程/原理,在不同實驗條件(濃度、溫度、時間、反應(yīng)物配比)下制備了不同形貌的ZnO微納米材料,系統(tǒng)探討了不同因素對其形貌和結(jié)構(gòu)的影響,并采用光致發(fā)光譜和紫外-可見光吸收光譜作為光學(xué)性能的表征手段。此外,以普通玻璃片為基底,采用一步水浴法制備出了微納米花形ZnO陣列及摻S微納米花形ZnO陣列,研究了摻S對花形ZnO陣列結(jié)構(gòu)、形貌與發(fā)光性能的影響。采用X-射線粉末衍射儀(XRD)進(jìn)行物相分析,場發(fā)射掃描電子顯微鏡(FESEM)透射電鏡(TEM,配有選區(qū)電子衍射(SAED))觀察產(chǎn)物的形貌,熒光光譜儀(激發(fā)光源為Xe燈)在室溫下測定光致發(fā)光(PL)光譜,紫外光譜儀分析樣品的紫外-可見光吸收光譜。研究結(jié)果表明: (1)微納米花形ZnO的花瓣為六角錐形結(jié)構(gòu),XRD測試表明其為纖鋅礦ZnO結(jié)構(gòu),高分辨透射電鏡及選區(qū)電子衍射花樣表明其為單晶結(jié)構(gòu),并且沿著從c軸生長,能譜分析表明其由Zn和O元素組成,組成接近1:1,表明其結(jié)晶良好。 (2)反應(yīng)溶液濃度、生長溫度、生長時間、反應(yīng)物配比等對樣品形貌的影響較大。隨著反應(yīng)溶液濃度的增大,微納米花形ZnO的生長速度加快,尺寸增加,結(jié)晶致密、晶體質(zhì)量提高。隨著生長溫度的降低,晶核易團(tuán)聚從而導(dǎo)致花瓣聚集;此外溫度的降低使反應(yīng)速率降低,并導(dǎo)致晶粒發(fā)育不完全。隨著生長時間的延長,初期有助于晶粒的發(fā)育和長大,但當(dāng)時間過長時,容易造成“溶解”現(xiàn)象,使晶體質(zhì)量下降。乙二胺的選擇性吸附提供了二次形核生長點,因此在形成花形ZnO結(jié)構(gòu)中起著決定性的作用,而六亞甲基四胺只是影響花瓣的形貌,吸附在花瓣側(cè)面阻礙其生長,使花瓣更為“修長”。 (3)微納米花形ZnO的PL譜中有兩個特征發(fā)光峰,分別是365 nm處的窄的紫外發(fā)射峰及406 nm左右寬的紫外-紫光發(fā)光峰。不同反應(yīng)條件(反應(yīng)溶液濃度、生長溫度、反應(yīng)物配比)對光致發(fā)光性能亦有影響。 (4)摻S微納米花形ZnO陣列較未摻微納米花形ZnO陣列的均勻性和取向性得到了提高,但表面變得粗糙,此外,摻S后產(chǎn)物的PL光譜的UV發(fā)射峰減弱且出現(xiàn)了較強(qiáng)的綠光發(fā)射峰。
[Abstract]:ZnO is an important II-IV direct wide band gap semiconductor materials at room temperature, the band gap is 3.37 eV, the high exciton binding energy of 60 meV, is considered to be a promising UV light emitting material. At the same time it is also a kind of multi functional oxide materials, photoelectric, piezoelectric, ferroelectric, pyroelectric that has excellent properties of the magnetic field, can be widely used in transparent electrodes, piezoelectric materials, varistors, acoustic wave devices and solar cells and other areas.
At present, ZnO research mainly focuses on the study of ZnO doped ZnO films, and ZnO nano structure. In nano structure field, researchers have made great progress, but the application of nano ZnO devices still have a long way to go. As everyone knows, the performance of the material depends on the structure of the material, and the material structure and depends largely on in the preparation method and process. Therefore, the material morphology, controllable preparation of size, for the application of nano ZnO devices is essential prerequisite.
This paper adopts the simple water bath method, using zinc nitrate (Zn (NO_3) _2 6H_2O six (four), methylene amine (CH_2) 6N_4) and ethylenediamine (C2H8N2) as raw materials, flowerlike ZnO structure were prepared to study the growth process / principle, in different experimental conditions (concentration, temperature that time, the ratio of reactants) with different morphologies of ZnO micro nano materials were prepared to investigate the effects of factors on the morphology and structure, and the photoluminescence spectra and UV Vis absorption spectroscopy was used to characterize the optical properties. In addition, the ordinary glass sheet as the substrate, the a water bath was prepared flowerlike ZnO arrays and S doped flowerlike ZnO arrays, studied S doped flowerlike ZnO arrays of structure, morphology and luminescent properties of influence. By X- - ray diffraction (XRD) phase analysis, field emission scanning electron microscope (FESEM) transmission (TEM, with electron microscope Selective electron diffraction (SAED) was used to observe the morphology of the products. Photoluminescence (PL) spectra were measured at room temperature with fluorescence spectrometer (excitation lamp as Xe lamp), and ultraviolet visible light absorption spectrum of samples was analyzed by ultraviolet spectrometer.
(1) flowerlike ZnO petals six pyramid structure, XRD test showed that the wurtzite structure of ZnO, indicating that the crystal structure of high resolution transmission electron microscopy and electron diffraction patterns, and along the growth from the c axis, energy spectrum analysis showed that the Zn and O elements, which is close to 1:1 that indicated that the crystal is good.
(2) the concentration of reaction solution, growth temperature, growth time, effect of reactant ratio on the morphology greatly. With the increase of the concentration of reaction solution, micro nano flowerlike ZnO growth rate accelerated, increase in size, compact crystal, crystal quality improved. With decreasing growth temperature, nucleation agglomerate resulting in petals in addition, aggregation; the decrease of the temperature reduces the rate of reaction, and the grains are not fully developed. With the extension of the growth time, early helps grain development and grow up, but when the time is too long, easily lead to "dissolve" phenomenon, the decline in the quality of crystal. The selective adsorption of ethylenediamine provides two nucleation and growth point therefore, in the form of play a decisive role in the flower shaped ZnO structure, and six methylene four amine only affect petal morphology, adsorption inhibited their growth in petals side, the petals is more slender.
(3) there are two characteristic peaks in the PL spectrum of ZnO, which are 365 nm narrow ultraviolet emission peak and 406 nm wide ultraviolet violet photoluminescence peak. Different reaction conditions (concentration of reaction solution, growth temperature and reactant ratio) also affect the photoluminescence property.
(4) the uniformity and orientation of S doped micro nano flower ZnO array were higher than that of the ZnO array without micro nano flower, but the surface became rough. In addition, the S emission peak of PL spectra of products decreased and a strong green emission peak appeared.

【學(xué)位授予單位】：中國海洋大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2011
【分類號】：TB383.1

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