104學年度：異質結構ZnO/MZnO(M=Mg,Ca)對ZnO電洞濃度穩定與提升及其於光降解應用上之研究
計畫名稱：異質結構ZnO/MZnO(M=Mg,Ca)對ZnO電洞濃度穩定與提升及其於光降解應用上之研究
執行起迄：2015/08/01~2017/07/31
總核定金額：1,935,000元
中文摘要：在計畫的第二年度，我們進行含氧化鋅鈣結構的電洞濃度特性研究。我們在玻璃與矽基板上製作不同鈣含量的氧化鋅鈣薄膜，以穿透與反射光譜來分析其能階變化，其能階隨著沉積前驅物中的鈣成分增加而增加。同時分析其表面形貌，晶體品質，以及導電濃度等特性。在電子顯微鏡下，其薄膜表面形貌呈現大小不一的片狀形貌。在結構上，主要為(101)晶向。在電性上，無摻雜的氧化鋅鈣薄膜呈現n型導電行為，而其電子濃度隨著鈣含量增加而增加。經由光激發螢光光譜分析，其深層能隙態造成的綠光放射乃隨鈣含量增加而增加，了解其導電差異可能為這些缺陷所主導。 而在進行氮以及銦氮共摻雜情況下，光激發螢光光譜的綠光放射受到明顯抑制，薄膜乃呈現p型導電行為。經由4個月的觀察，氮摻雜的氧化鋅鈣薄膜呈現電洞濃度微減的行為(1.9x1016cm-3 – 9.0x1015 cm-3 )，而銦氮共摻雜的氧化鋅鈣薄膜的電洞濃度呈現穩定的情況(1.2x1019cm-3 – 9.7x1018 cm-3)。顯示銦氮共摻雜有助於維持氧化鋅鈣薄膜的p型導電狀況。將此結構應用到氧化鋅鈣/氧化鈣異質結構，而於氧化鋅鈣區域進行銦氮共摻雜，其結構之電洞濃度穩定情況與單層的結果相似。在應用於光催化時，此銦氮共摻雜氧化鋅鈣的情況與之前銦氮共摻雜氧化鋅鎂情況類似:具有銦氮共摻雜氧化鋅鈣異質結構的的降解能力最差。其原因可能為銦氮共摻雜抑制了薄膜深層能態的形成，提高了電洞有效摻雜量，以及減少了藉由深層能態的光吸收，而使光降解能力變差。而各式具氧化鋅鈣結構薄膜樣品的光降解能力雖不同，在貯存一個月後，其光降解能力均呈現下降情況。而不同樣品之下降程度相近，顯示這可能是在貯存期間的樣品表面變化所致。
英文摘要：In the second stage of the project, the calcium zinc oxide (CaZnO) films with different calcium/zinc (Ca/Zn) ratio were fabricated on glass and Si substrate. The optical bandgap of the CaZnO films deposited on glass substrate was investigated. The bandgap increases with the increasing of Ca/Zn ratio in precursors. The incorporation efficiency of Ca into the CaZnO film is low. Film morphology, crystallinity, carrier concentration etc. were characterized. Different flake type morphology with preferred (101) crystalline orientation can be characterized for these CaZnO films. N-type conduction of these CaZnO films was identified with Hall measurement. The electron concentration increases with the increasing of Ca content. With photoluminescence analysis, the deep level state related green emission increases with the increasing of Ca content also. The n-type conduction may be contributed from these defects. For nitrogen (N) and indium, nitrogen (In,N) codoping into the film, the green emission was inhibited and p-type conduction were appeared. With the four month preservation, the hole concentration decreases from 1.9x1016cm-3 – 9.0x1015 cm-3 for N-doped ZnO and remains around 1.2x1019cm-3 – 9.7x1018 cm-3 for In,N-codoped ZnO. Similar hole concentration variation behavior was characterized for the In,N codoped heterostructured CaZnO/ZnO. While applying these films in photocatalyst, the codoped heterostructured films show the worse photocatalytic ability. The resuolt is similar to that of magnesium zinc oxide films. As the In,N codoping may inhibit the formation of deep level states, thus cause the hole concentration enhancement by the reduction of carrier compensation, and cause the reduction of photodegradation ability. The photodegradation ability of the film degraded after one month preservation. The degradation ratio for these CaZnO-based films is similar. This implies the degradation is caused by the surface variation in preservation.
執行起迄：2015/08/01~2017/07/31
總核定金額：1,935,000元
中文摘要：在計畫的第二年度，我們進行含氧化鋅鈣結構的電洞濃度特性研究。我們在玻璃與矽基板上製作不同鈣含量的氧化鋅鈣薄膜，以穿透與反射光譜來分析其能階變化，其能階隨著沉積前驅物中的鈣成分增加而增加。同時分析其表面形貌，晶體品質，以及導電濃度等特性。在電子顯微鏡下，其薄膜表面形貌呈現大小不一的片狀形貌。在結構上，主要為(101)晶向。在電性上，無摻雜的氧化鋅鈣薄膜呈現n型導電行為，而其電子濃度隨著鈣含量增加而增加。經由光激發螢光光譜分析，其深層能隙態造成的綠光放射乃隨鈣含量增加而增加，了解其導電差異可能為這些缺陷所主導。 而在進行氮以及銦氮共摻雜情況下，光激發螢光光譜的綠光放射受到明顯抑制，薄膜乃呈現p型導電行為。經由4個月的觀察，氮摻雜的氧化鋅鈣薄膜呈現電洞濃度微減的行為(1.9x1016cm-3 – 9.0x1015 cm-3 )，而銦氮共摻雜的氧化鋅鈣薄膜的電洞濃度呈現穩定的情況(1.2x1019cm-3 – 9.7x1018 cm-3)。顯示銦氮共摻雜有助於維持氧化鋅鈣薄膜的p型導電狀況。將此結構應用到氧化鋅鈣/氧化鈣異質結構，而於氧化鋅鈣區域進行銦氮共摻雜，其結構之電洞濃度穩定情況與單層的結果相似。在應用於光催化時，此銦氮共摻雜氧化鋅鈣的情況與之前銦氮共摻雜氧化鋅鎂情況類似:具有銦氮共摻雜氧化鋅鈣異質結構的的降解能力最差。其原因可能為銦氮共摻雜抑制了薄膜深層能態的形成，提高了電洞有效摻雜量，以及減少了藉由深層能態的光吸收，而使光降解能力變差。而各式具氧化鋅鈣結構薄膜樣品的光降解能力雖不同，在貯存一個月後，其光降解能力均呈現下降情況。而不同樣品之下降程度相近，顯示這可能是在貯存期間的樣品表面變化所致。
英文摘要：In the second stage of the project, the calcium zinc oxide (CaZnO) films with different calcium/zinc (Ca/Zn) ratio were fabricated on glass and Si substrate. The optical bandgap of the CaZnO films deposited on glass substrate was investigated. The bandgap increases with the increasing of Ca/Zn ratio in precursors. The incorporation efficiency of Ca into the CaZnO film is low. Film morphology, crystallinity, carrier concentration etc. were characterized. Different flake type morphology with preferred (101) crystalline orientation can be characterized for these CaZnO films. N-type conduction of these CaZnO films was identified with Hall measurement. The electron concentration increases with the increasing of Ca content. With photoluminescence analysis, the deep level state related green emission increases with the increasing of Ca content also. The n-type conduction may be contributed from these defects. For nitrogen (N) and indium, nitrogen (In,N) codoping into the film, the green emission was inhibited and p-type conduction were appeared. With the four month preservation, the hole concentration decreases from 1.9x1016cm-3 – 9.0x1015 cm-3 for N-doped ZnO and remains around 1.2x1019cm-3 – 9.7x1018 cm-3 for In,N-codoped ZnO. Similar hole concentration variation behavior was characterized for the In,N codoped heterostructured CaZnO/ZnO. While applying these films in photocatalyst, the codoped heterostructured films show the worse photocatalytic ability. The resuolt is similar to that of magnesium zinc oxide films. As the In,N codoping may inhibit the formation of deep level states, thus cause the hole concentration enhancement by the reduction of carrier compensation, and cause the reduction of photodegradation ability. The photodegradation ability of the film degraded after one month preservation. The degradation ratio for these CaZnO-based films is similar. This implies the degradation is caused by the surface variation in preservation.
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