本實驗在Cu2ZnSnSe4(CZTSe)相關部分，分別在高壓釜中使用溶熱法以及以濕式化學法在迴流系統中合成CZTSe以及Cu2CdSnSe4(CCTSe)奈米晶，探討不同的反應溶劑、反應前驅物的莫爾比、反應溫度、反應時間及不同的反應前驅物對合成CZTSe以及CCTSe奈米晶的影響以及產物的光學性質。CZTSe、CCTSe在高壓釜的反應中添加聯胺，可以較未添加聯胺的反應更易獲得較純的產物，減少二元(ZnSe、Cu2-xSe、CdSe)及三元(Cu2SnSe3)雜相的生成，這是因為聯胺具有使金屬硫系化合物在溶熱反應中降維度(dimensional reduction)之功能有，添加聯胺明顯有助於反應。而濕式化學法在迴流系統中合成CZTSe系列，使用醋酸鋅作為鋅的前驅物相較以氯化鋅為前驅物容易獲得較純的產物，這是因為醋酸根離子具有螯合的作用，有助於金屬離子的結合並促進反應的進行。
透過液相化學合成以及後續的旋轉塗佈分別製備Sn1-xGexS和Sn1-xSbxS薄膜。Ge和Sb在SnS中的取代溶解度分別為約6和5 at%。 Sn1-xGexS和Sn1-xSbxS薄膜的可調控能隙分別在1.25-1.35eV 和1.30-1.39 eV的範圍內。本研究並探討了Sn1-xGexS和Sn1-xSbxS薄膜可調控能隙的可能機制。對於在N2中在200-350 ℃進行退火的Sn1-xGexS和Sn1-xSbxS薄膜，200 ℃退火的膜的能隙保持不變，而300℃和350℃退火的膜的能隙隨著退火溫度上升而下降，其原因分別為Ge和Sb的損失。
在液相化學合成系統中在反應溫度230-275 ℃反應5-36小時合成的Sn1-xSbxSe (0≤x≤0.6)奈米晶體，並探討形態的轉變和能隙變化。Sn2+對Se2-具有比Sb3+更強的反應性。SnSe(1)相(JCPDS 01-075-6133)在Sn1-xSbxSe (0≤x≤0.2)奈米晶體中生長，而SnSe(2)相(JCPDS 32-1382)在Sn1-xSbxSe (0.3≤x≤0.6)奈米晶體中生長。在本研究中，Sb在SnSe晶格中的置換溶解度約為10 at%。在Sn1-xSbxSe (0.3≤x≤0.6)奈米晶體中摻雜更多的Sb在其中引起更多的缺陷，從而導致從SnSe(1)到SnSe(2)的相變。 SnSe奈米晶體作為奈米片生長，而Sb的引入增強了Sn1-xSbxSe奈米棒的生長。通過將Sb濃度(x)從0增加到0.2，Sn1-xSbxSe (0≤x≤0.2)奈米晶體的直接和間接能隙可以分別從1.39至1.53 eV和0.93至1.28 eV進行調節。Sn1-xSbxSe奈米晶體的可調變形態和能隙使其成為有潛力的光伏材料。
CuInS2(CIS)奈米線的部分，以放電紡絲法製備CIS前驅物高分子奈米纖維，結合水熱法以高分子奈米纖維作為高分子型離子釋放源(polymer-type ion release source, PIRS)，在高壓釜中合成CIS奈米線。過去尚未有過結合兩種方法製備CIS奈米線的相關報告，本研究探討高分子濃度對於前驅物奈米纖維形貌及均勻度的影響，以及探討PIRS在水熱法中運作的反應機制，在水熱法中維持穩定且低離子濃度，使產物具有較高的方向選擇性。

The effects of hydrazine on the synthesis of Cu2ZnSnSe4 (CZTSe) and Cu2CdSnSe4 (CCTSe) nanocrystals in an autoclave as a function of temperature and time were explored. On heating at 190 °C for 24-72 h, pure CZTSe and CCTSe nanocrystals could readily grow in the hydrazine-added solution, while in the hydrazine-free solution the intermediate phases such as ZnSe, Cu2Se, and Cu2SnSe3, and Cu2SnSe3 and CdSe associated with the CZTSe and CCTSe nanocrystals grew, respectively. This result reveals that hydrazine can speed up the synthesis of pure CZTSe and CCTSe nanocrystals via a solvothermal process. The mechanisms for the hydrazine-enhanced growth of CZTSe and CCTSe nanocrystals were discussed. The pure CZTSe and CCTSe nanocrystals were subsequently fabricated to the smooth films by spin coating without further annealing in the selenium atmosphere. This processing may be beneficial to the fabrication of the absorber layer for solar cells and thermoelectric devices. In addition, the effects of different Zn precursors on the synthesis of pure and stoichiometric CZTSe nanocrystals via a facile solvothermal process were explored. The products were characterized using X-ray diffraction, Raman spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, and UV-vis spectroscopy. The present study showed that with the Zn(CH3COO)2 precursor pure and stoichiometric CZTSe nanocrystals were readily synthesized, while with the ZnCl2 precursor the synthesized nanocrystals were Zn-deficient and composed of CZTSe and Cu2SnSe3 phases. This result can be attributed to the chelating effect of the acetate anion in the solvothermal reaction.
Ge- and Sb-doped SnS films with single orthorhombic SnS phase were fabricated via solvothermal routes and subsequent spin-coating, respectively. The substitution solubilities of Ge and Sb in SnS are about 6 and 5 at.%, respectively. The bandgaps of Sn1-xGexS and Sn1-xSbxS films can be tuned in the ranges of 1.25-1.35 and 1.30-1.39 eV, respectively. The possible mechanisms for the tunable bandgaps of Sn1-xGexS and Sn1-xSbxS films are discussed. For the Sn1-xGexS and Sn1-xSbxS films subjected to annealing at 200-350 °C in N2, the bandgaps of 200 °C-annealed films remain unchanged, while those of 300 °C- and 350 °C-annealed films decrease with the annealing temperature because of the evaporation of Ge and Sb respectively.
The phase formation, morphology evolution and bandgap of Sn1−xSbxSe (0 ≤ x ≤ 0.6) nanocrystals synthesized at 230–275 °C for 5–36 h in a one-pot system were studied. Sn2+ is kinetically more reactive than Sb3+ toward Se2−. The SnSe(1) phase (JCPDS 01-075-6133) grew in the Sn1−xSbxSe (0 ≤ x ≤ 0.2) nanocrystals, while the SnSe(2) phase (JCPDS 32-1382) was dominant in the Sn1−xSbxSe (0.3 ≤ x ≤ 0.6) nanocrystals. In the present study, the substitution solubility of Sb in the SnSe lattice is about 10 at%. The introduction of more Sb in the Sn1−xSbxSe (0.3 ≤ x ≤ 0.6) nanocrystals induced more defects therein and thus caused the phase transformation from SnSe(1) to SnSe(2). The SnSe nanocrystals grew as nanosheets, while the introduction of Sb enhanced the growth of Sn1−xSbxSe nanorods. The direct and indirect bandgaps of the Sn1−xSbxSe (0 ≤ x ≤ 0.2) nanocrystals could be tuned from 1.39 to 1.53 eV and 0.93 to 1.28 eV, respectively, by increasing the Sb concentration (x) from 0 to 0.2. The tunable morphology and bandgap of the Sn1−xSbxSe nanocrystals make them potential candidates as photovoltaic materials.
Chalcopyrite copper indium sulfide (CuInS2, CIS) has a bandgap that is optimal for a solar energy conversion material. The CIS nanowires were synthesized in a hydrothermal system by using a polymer-type ion release source to control the precursor concentration. The results indicate that the reaction process is based on the formation of CuS binary compound, which is then followed by indium intercalation, finally forming the CIS chalcopyrite crystal structure. The products were characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The CIS nanowires were 100–300 nm in diameter and 2–5 μm in length.

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