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The Raman spectrum shows the expected vibrational modes at 131, 306, 370, 493, and 628 cm−1, which is an unambiguous signature of the cubic In2O3 structure. The factor group analysis predicts 4Ag (Raman) + 4Eg (Raman) + 14Tg (Raman) + 5Au (inactive) + 5Eu (inactive) + 16Tu (IR) modes for cubic In2O3 [21]. The modes observed here correspond to bcc-In2O3, agreeing well with the values reported in the literatures [22, 23]. The Raman results further evidence the good crystallinity of cubic In2O3 nanoplatelets. This suggests the obtained In2O3 nanoplatelets would promise application in sensor with high sensitivity and stability since the microstructure broken (especially at higher temperature) can be avoided owing to the good crystallinity. Optical absorption experiments were also carried out to elucidate the band gap energy, which is one of the most important electronic parameters for semiconductor nanomaterials. Fig. 6 shows a typical UV-vis absorption spectrum of the In2O3 nanoplatelets. In2O3 is an n-type semiconductor, and its optical band gap can be estimated using the following formula: (αhν)n = B(hν − Eg) (1) where, α is the absorption coefficient, hν is the photon energy, B is a constant characteristic of the material, Eg is the band gap, and n is either 1/2 for an indirect transition or 2 for a direct transition. The (αhν)2 versus hν curve for the product is shown in the inset in Fig. 6. Extrapolation of the linear portion of the curve to α = 0 gives the optical band gap value of 3.1 eV for the In2O3 nanoplatelets. In addition, the best fit of Eq. (1) to the absorption spectrum of the product gives n = 2, suggesting that the as-obtained In2O3 nanoplatelets are semiconducting with a direct transition at this energy. Among the published reports, the band gap of In2O3 calculated varied from 2.3 to 3.8 eV, such as 3.7 eV for bulk In2O3 [24], 3.4 and 3.8 eV for In2O3 films [25], 3.2 eV for undoped In2O3 films [26], 2.6 eV for In2O3 nanoparticles [27]. Although the reason for the big band-gap change of In2O3 is not still clear, the stoichiometry, crystallinity and density of oxygen vacancies in In2O3 should have an effect on the band gap, and a special study may be necessary to clarify this issue. |
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拉曼光譜顯示期望的振動(dòng)峰在131, 306, 370, 493, and 628 cm−1,這很明顯符合In2O3的立方結(jié)構(gòu),群因素分析預(yù)測(cè)對(duì)于立方In2O3 [21]有著4Ag (Raman) + 4Eg (Raman) + 14Tg (Raman) + 5Au (inactive) + 5Eu (inactive) + 16Tu (IR)的關(guān)系。觀測(cè)到的峰符合bcc-In2O3,與文獻(xiàn)報(bào)道中的一致[22, 23]。拉曼光譜進(jìn)一步證實(shí)了In2O3納米片有著較好的晶相。這意味著得到的In2O3納米片由于其好的晶型會(huì)保證在傳感器的應(yīng)用中有高的靈敏度和穩(wěn)定性除非微孔結(jié)構(gòu)被破壞(尤其在較高的溫度下)。 同時(shí)進(jìn)行的光學(xué)吸附實(shí)驗(yàn)也說(shuō)明了對(duì)于半導(dǎo)體材料來(lái)說(shuō)是很重要的一個(gè)電學(xué)參數(shù):帯隙能。圖6是一個(gè)典型的In2O3納米片紫外吸收光譜圖。In2O3是n型半導(dǎo)體,其帶寬可以用下面公式計(jì)算: (αhν)n = B(hν − Eg) (1) 其中a是吸附系數(shù),hv是光子能,B是材料的固定特性參數(shù),Eg是帶寬,n是間接帯隙的一半或者是直接帯隙的2倍。(αhν)2對(duì)hv的曲線見圖6,。由該曲線的線性部分外推算得In2O3納米片的帶寬為2.1eV。另外,當(dāng)n=2該材料的的紫外吸收光譜用方程1擬合最合適,意味著得到的In2O3納米片半導(dǎo)體在該能量處有這直接帯隙。在已有的報(bào)道中,算得的n2O3納米片的帶寬從2.3到3.8 eV都有,比如體材料的In2O3 [24]帯隙寬為3.7eV,In2O3膜的帯隙寬分別為3.4和3.8 eV [25],為摻雜的In2O3膜的帯隙寬為3.2eV [26],In2O3納米粒子的帯隙寬為2.6eV [27].盡管In2O3帯隙寬變化之大的原因還不清楚,化學(xué)計(jì)量,晶型以及In2O3中O缺陷都會(huì)對(duì)其有重要影響,仍有必要進(jìn)行一些特別的實(shí)驗(yàn)來(lái)弄清該問題。 |
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