本研究探討CuCo2O4之相變化及摻雜鎳效應對於結構及光電特性的影響，實驗分成兩部分，第一階段將薄膜退火於250℃至450℃，研究結構變化及光電特性，分析確認最佳製程溫度是350℃；第二階段以最佳製程溫度製備摻雜鎳於CuCo2O4，形成Cu(Co1-xNix)2O4 (x＝0.05、0.10、0.15、0.20、0.25及0.30)薄膜，鑑定以摻雜比例為Nix=0.15具有最佳的導電性質，薄膜退火於250℃至350℃，薄膜均為單一相尖晶石CuCo2O4，在400℃及450℃薄膜為複合相特性，鎳摻雜於CuCo2O4薄膜並未改變薄膜晶體結構且無雜相的形成，CuCo2O4薄膜退火溫度於250 ℃增加至450℃的晶粒尺寸由3.32 nm增加至13.77 nm，但鎳摻雜使得CuCo2O4平均晶粒尺寸由6.32 nm (Nix=0)減少至4.22 nm (Nix=0.30)，薄膜的表面散佈大小不一的凸起狀結構，隨著退火溫度的增加凸起狀物有增大趨勢，然而隨著摻鎳的比例增加凸起物有逐漸縮小狀態；表面粗糙度分析顯示當鎳摻雜比例大於含量20%時會造成奈米裂縫的形成，使得粗糙度增加。退火於250 ℃至450℃的CuCo2O4薄膜透光率曲線相似，將鎳摻雜於CuCo2O4薄膜的比例大於10%會產生透光性質的紅移效應(Red-shift) ，奈米晶粒尺寸增加效應，造成退火由250℃增加至350℃單一相CuCo2O4薄膜能隙由3.98 eV減少至3.58 eV，鎳摻雜效應會使得CuCo2O4薄膜能隙由3.58 eV下降至2.68 eV，退火於350℃本質薄膜具有最佳導電特性，電阻率為5.66 Ω-cm，載子濃度為4.14x1014 cm-3，以製程500℃溫度製備摻雜鎳比例由0.05增加至0.30，分析顯示鎳15%有最低之電阻率為0.187 Ω-cm，載子濃度為9.59x1016 cm-3，藉由鎳摻雜於CuCo2O4薄膜可以有效提升導電特性及載子濃度，所有薄膜均為P型半導體特性，Ni-doped CuCo2O4可以為抗菌應用。
The effects of CuCo2O4 phase change and nickel doping on the structure and photoelectric properties were investigated. The experiment was divided into two parts. In the first stage, the films were annealed from 250°C to 450°C to study structural changes and photoelectric properties. The analysis confirmed that 350°C was the optimum annealing temperature. The second stage, we prepared nickel-doped CuCo2O4 at the temperature of 350°C to form Cu(Co1-XNix)2O4 (X=0.05, 0.10, 0.15, 0.20, 0.25 and 0.30) films, which identified for doping effects. The ratio of Nix=0.15 has the best film’s conductivity. The films were annealed from 250°C to 350°C with single phase CuCo2O4. The composite phase characteristics were in 400°C and 450°C films. Nickel were doped in CuCo2O4 films where no impurity phase was formed. The annealing temperatures increased from 250°C to 450°C that grain sizes increased from 3.32 nm to 13.77 nm. Nickel doping made CuCo2O4 films’ average grain size from 6.32 nm (Nix=0) reduced to 4.22 nm (Nix = 0.30). The surface of the film has a polygonal appearance. With the increase of annealing temperature, the size of protrusion microstructure has an increasing tendency. Surface roughness analysis showed that the nickel doping ratio was greater than 20%, in which the nano-cracks formed and the roughness increased. Surface features without significant change after the Ni doping. The transmittance curves of CuCo2O4 films annealing from 250°C to 450°C are similar. The ratio of nickel doping to CuCo2O4 film was greater than 0.10, which showed a red-shift effect of light transmission. With annealing temperatures increased from 250°C to 350°C, band gaps reduced from 3.98 eV to 3.58 eV. Nickel doping effects make the films’ energy gaps from 3.58 eV to 2.68 eV. Annealed-350°C film has a lower resistivity of 5.66 (Ω-cm), carrier concentration of 4.14x1014 cm-3. Preparation ratio of Ni doping increased from 0.05 to 0.30, analysis showed that nickel ratio was 0.15 with the lowest resistivity of 0.18 (Ω-cm), the carrier concentration was 9.59x1016 cm-3. Conductivity and carrier concentration can be effectively improved by doping the CuCo2O4 film with nickel. All the films are p-type semiconductor characteristics, and Ni-doped CuCo2O4 can be used as a candidate for optoelectronic component applications.
