臺灣博碩士論文加值系統

本研究是以氯化鈉和氯化銅化合物共同作為氯離子的前驅物，而氯化銅亦同時為銅離子的前驅物，使用化學浴沉積法在銅基板上製備氯化亞銅薄膜。藉由改變實驗參數，如：摻入濃度、沉積時間、鹽酸浸漬...等，製備不同條件下沉積的氯化亞銅薄膜，通過分析它們的導電型態、光學特性、晶相結構、表面形貌、元素組成以及結構層，進行有系統地比較，尋找出最適當沉積參數及其特性研究，並且與使用單一氯化銅化合物為前驅物所製備出的氯化亞銅薄膜作比較。
首先是研究在不同濃度氯化鈉的摻入下對氯化亞銅薄膜之影響，並且與未摻入時所製備出的薄膜進行比較。所製備的薄膜之發光特性、晶相結構、表面形貌以及元素組成已經過詳細審查。從分析結果得知以氯化鈉與氯化銅化合物為兩種離子源前驅物下的良好品質之氯化亞銅薄膜已經通過化學浴沉積法實現，並且確認摻入比未摻入氯化鈉所製備出的薄膜之品質更好。藉此結果可證實以氯化鈉化合物增加氯離子源的理論是成功，有達成改善氯化亞銅薄膜中氯原子相對比率之狀況。
然後是研究改變薄膜沉積時間與鹽酸浸漬次數對氯化亞銅薄膜之影響。所製備的薄膜之發光特性、晶相結構、表面形貌、元素組成以及結構層已經過詳細審查。從分析結果發現未改變樣品所製備出的是平坦連續的氯化亞銅覆蓋層，薄膜厚度約為2微米，比未摻入氯化鈉所製備出的薄膜厚約1微米，並且其薄膜層是純的氯化亞銅結晶，與其相應的元素分佈是均勻的。另外，雖然延長薄膜沉積時間與增加鹽酸浸漬次數所製備出的是不連續的氯化亞銅覆蓋層（60min-3dipping、80min-4dipping），但是其品質並不輸於未摻入氯化鈉所製備出的薄膜，所以如此改變所製備出的氯化亞銅薄膜可以依照往後所要製成的元件之需求調整其結構層。藉此結果可證實增厚薄膜以減少Cu^+離子的形成的理論是成功，亦有達成改善氯化亞銅薄膜中氯原子相對比率之狀況。
另一方面為了改善薄膜之晶相品質，本研究也調查了在不同溫度與時間的熱退火處理下對氯化亞銅薄膜之影響。所製備的薄膜之導電型態、發光特性、晶相結構、表面形貌以及元素組成已經過詳細審查。從分析結果得知回火前、後所製備出的皆是n型氯化亞銅薄膜，並且發現薄膜的發光強度、結晶性、表面氯元素含量會隨著溫度提升而增加（150℃-1hr、200℃-1hr），再加上其表面形貌會也隨著溫度與時間的提升而更趨於平整，藉由上述分析結果證實熱退火處理是有助於提升氯化亞銅薄膜品質。值得一提的是於光激螢光光譜圖中觀察到在5.7K低溫下激子和雙激子的發光機制，特別是於室溫下明顯地觀察到自由激子的發射，而此特性意謂薄膜品質佳。以上分析結果對於氯化亞銅未來用以製備二極體元件有著重大的意義。


關鍵字：氯化鈉、氯化銅、氯化亞銅、化學浴沉積法、銅基板

*：作者
**：指導老師

This research is taking both sodium chloride (NaCl) and copper (II) chloride (CuCl_2) compound as precursor of chloride ions, while CuCl_2 is also taken as precursor of copper ions, and using chemical bath deposition (CBD) to prepare copper (I) chloride (CuCl) films on a copper (Cu) substrate. We prepare CuCl films deposited under different conditions by changing the parameters of the experiment, such as adding concentration, deposition time, hydrochloric acid (HCl) dip, etc. By analyzing their electrical properties, optical properties, phase structure, morphology of the surface, elemental composition and structure layer, we can conduct a systematic comparison to find out the most suitable deposition parameters and researches of their characteristics. Then we compare with the CuCl films prepared by using single CuCl_2 compound as precursor.
First, we study the effect on the CuCl film grown with adding different concentrations of NaCl, and compared with the one grown with not adding NaCl. The light emission characteristics, phase structure, morphology of the surface and elemental composition of prepared films have detailed investigated. We can know from the analysis result that a good-quality CuCl film was achieved by CBD via taking NaCl and CuCl_2 compound as precursor of two kinds of ions source. And we confirmed the quality of the film grown with adding NaCl is better than the one without adding NaCl. We can prove the theory that using NaCl compound to increase chloride ions is successful by this result and we have achieved that improving relative ratio of chloride atoms in CuCl film.
Next, we study the effect on the CuCl film grown with changing the deposition time of the film and HCl dip times. The light emission characteristics, phase structure, morphology of the surface, elemental composition and structure layer of prepared films have detailed investigated. We found the prepared CuCl-covered layer of simples without changing is flat and continuous from the analysis result. The thickness of the film is about 2 microns and about 1 micron thicker than the one without adding NaCl. Its film layer is pure CuCl crystallites and corresponding elemental distribution is uniform. In addition, although the film grown with extending deposition time of the film and increasing HCl dip times is discontinuous CuCl-covered layer (60min-3dipping and 80min-4dipping), its quality is not worse than the one without adding. So the CuCl film prepared by this changing can adjust its structure layer depending on the demand of devices need to fabricate afterwards. We can prove the theory that increasing the thickness of the film to decrease the formation of Cu^+ is successful by this result and also have achieved that improving relative ratio of chloride atoms in CuCl film.
On the other hand, in order to improve the quality of phases of the film, this research also investigated the effect on the CuCl film under different temperature and time of the thermal annealing treatment. The light emission characteristics, phase structure, morphology of the surface, elemental composition and structure layer of prepared films have detailed investigated. We can know from the analysis result that the CuCl films prepared before- and after-annealing are all n-type and find the intensity of light emission, crystalline and contents of chloride on the surface of the film will increase with the temperature increasing (150℃-1hr and 200℃-1hr). And plus, its morphology of the surface also tends to be more flat with temperature and time increasing. We can prove the thermal annealing treatment is helpful to enhance the quality of CuCl film by the analysis results described above. Noticeably, we observed light emission mechanism of exciton and bi-exciton in low temperature photoluminescence (PL) spectra at 5.7K, especially, clearly observed the free exciton related emission at room temperature and this property means the quality of the film is good. The analysis results above have great significance for CuCl used in the fabrication of the diode elements in the future.


Keywords: Sodium chloride (NaCl), copper (II) chloride (CuCl_2), copper (I) chloride (CuCl), chemical bath deposition (CBD), copper (Cu) substrate.

*: The author
**: The advisors

Content

摘要 I
Abstract IV
致謝 VI
Content VIII
List of Figures X
List of Tables XII
Chapter 1 Introduction 1
1.1 Intro 1
1.2 Wide band gap semiconductor materials 1
1.3 Characteristic of CuCl Material 2
1.4 Current researches of CuCl 3
1.5 Motivation of investigation 7
Reference 9
Chapter2 Theorem background and experiment system 12
2.1 Chemical Bath Deposition (CBD) 12
2.1.1 Ion-ion deposition 13
2.1.2 Cluster-cluster deposition 13
2.2 Hot probe 15
2.3 X-Ray Diffraction (XRD) 16
2.4 Photoluminescence (PL) 19
2.5 Scanning Electron Microscopy (SEM) 21
2.6 Energy Dispersive Spectroscopy (EDS) 22
2.7 X-ray Photoelectron Spectroscopy (XPS) 23
2.8 Dual Beam Focused Ion Beam (DB-FIB) 25
Reference 27
Chapter 3 Experiment 28
3.1 Experimental materials 28
3.2 Experimental procedure 28
Reference 33
Chapter 4 results and discussion 35
4.1 Simultaneously using sodium chloride and copper (II) chloride compound to prepare CuCl film 35
4.1.1 Photoluminescence (PL) - optical properties analysis 35
4.1.2 X-ray diffraction (XRD) - crystal structure analysis 40
4.1.4 X-ray Photoelectron Spectroscopy (XPS) - depth profiling 48
4.2 Change deposition time 56
4.2.1 Photoluminescence (PL) - optical properties analysis 57
4.2.2 X-ray diffraction (XRD) – crystal structure analysis 61
4.2.4 X-ray Photoelectron Spectroscopy (XPS) - depth profiling 68
4.2.5 Dual Beam Focused Ion Beam (DB-FIB)-cross-sectional observation and analysis 75
Reference 79
Chapter 5 Conclusion 80


List of Figures

Fig 1-1 Zinc blende structure of CuCl [18] 2
Fig.2-1 Process of ion-ion deposition 13
Fig.2-2 Schematic diagram of cluster-cluster deposition 14
Fig.2-3 Schematic diagram of CBD instrument 15
Fig.2-4 Schematic diagram of thermoelectric effect 15
Fig.2-5 Schematic diagram of hot probe measurement 16
Fig.2-6 Operating principle of X-ray tube 17
Fig.2-7 Schematic geometric diagram of lattice diffraction and Bragg equation 18
Fig.2-8 XRD diffraction instrument (model：Bruker AXS, D8-advance) 19
Fig.2-9 Process of photoluminescence at band edge 20
Fig.2-10 Schematic diagram of photoluminescence measurement system 21
Fig.2-11 Schematic diagram of scanning electron microscope 22
Fig.2-12 Principle of generating characteristic X-ray 23
Fig.2-13 Schematic diagram of the X-ray photoelectron spectroscopy 24
Fig.2-14 Schematic diagram of principle of XPS 25
Fig.2-15 Schematic diagram of etching and deposition principle 26
Fig.3-1 Schematic diagram of structure of sample 28
Fig.3-2 Schematic diagram of experimental process 29
Fig.3-3 Schematic diagram of experimental process 29
Fig.3-4 Digital electronic analysis balance 30
Fig.3-5 Schematic diagram of growth of chemical bath deposition 31
Fig.3-6 Schematic diagram of principle of CuCl film deposition 31
Fig.3-7 Alloying Furnace (Rapid thermal anneal system) 33
Fig.3-8 The measurement items of the experiments and the condition of the instruments 33
Fig.4-1 Comparing diagram of PL spectra of samples prepared with not adding and adding different concentrations of NaCl 39
Fig.4-2 Comparing diagram of FWHM values of PL spectra of samples prepared with not adding and adding different concentrations of NaCl 40
Fig.4-3 Comparing diagram of XRD patterns of samples prepared with not adding and adding different concentrations of NaCl 41
Fig.4-4 Schematic diagram of trend of intensity ratio changing of PL and XRD 43
Fig.4-5 Typical wide-scan XPS spectra selected of A3, A4 and A9 samples 50
Fig.4-6 Cu2p, Cl2p, O1s and Na1s core area of high resolution XPS spectra of A3, A4 and A9 samples 52
Fig.4-7 Distribution diagram of elemental composition of XPS depth analysis of A3, A4 and A9 samples 55
Fig.4-8 Comparing distribution diagram of elemental composition of XPS depth analysis of A3 and A9 samples 55
Fig 4-9 Comparing diagram of PL spectra of samples which are changed deposition time of A3 sample 60
Fig 4-10 Comparing diagram of PL spectra of samples which are changed deposition time of A9 sample 60
Fig 4-11 XRD patterns of B1, B3, B5 and B6 samples 62
Fig 4-12 Comparing diagram of XRD patterns of B1, B3, B5 and B6 samples 63
Fig.4-13 Typical wide-scan XPS spectra selected of B1, B3, B5 and B6 samples 70
Fig.4-14 Cu2p and Cl2p high resolution XPS spectra of B1, B3, B5 and B6 samples 71
Fig.4-15 Distribution diagram of elemental composition of XPS depth analysis of B1, B3, B5 and B6 samples 74
Fig.4-16 Comparing distribution diagram of elemental composition of XPS depth analysis of B1, B3, B5 and B6 sampples 74
Fig.4-17 Schematic diagram of formation process of structure layers 78


List of Tables

Table 1-1 Properties of wide band gap semiconductor material [1]~[17] 1
Table 1-2 material properties of CuCl [19] 3
Table 1-3 literatures of choices of substrates 4
Table 1-4 representative preparation of CuCl films and the contribution of research 5
Table 2-1 Common lattice extinction conditio 18
Table 4-1 Parameters tables of samples which are not adding and adding different mole concentrations of sodium chloride 35
Table 4-2 PL spectra of the samples prepared with adding higher concentrations of NaCl 36
Table 4-3 PL spectra of separately using single solution of NaCl to grow and purely copper substrates 37
Table 4-4 PL spectra of samples prepared with not adding and adding different concentrations of NaCl 38
Table 4-5 The intensity ratio of PL spectra of samples prepared with not adding and adding different concentrations of NaCl 40
Table 4-6 Intensity ratio of XRD patterns of samples prepared without and with adding different concentrations of NaCl 42
Table 4-7 SEM top view of samples prepared without and with adding different concentrations of NaCl 44
Table 4-8 Data of surface EDS analysis of samples prepared without and with adding different concentrations of NaCl, the unit used is atomic percentage (Atomic%) 45
Table 4-9 Data of surface EDS analysis of A3 sample, the unit used is atomic percentage (Atomic%) 47
Table 4-10 Parameters tables of A3 and A9 sample whose deposition time are changed 57
Table 4-11 PL spectra of samples which are changed deposition time 58
Table 4-12 The intensity ratio of XRD of B1, B3, B5 and B6 samples 63
Table 4-13 SEM top view of B1, B3, B5 and B6 samples 64
Table 4-14 SEM top view of zooming in different scale of B1 and B6 samples 65
Table 4-15 Data of surface EDS analysis of B1, B3, B5 and B6 samples, the unit used is atomic percentage (Atomic%) 66
Table 4-16 Data of DB-FIB analysis of B1 and B6 samples. (a-1) and (a-1): SEM top view. (b-1) and (b-2): Cross-sectional image of SEM. (c-1) and (c-2): Magnified image of marked region in image (b) 76
Table 4-17 Data of EDS analysis of denoted region or position in cross-sectional image of B1 sample, the unit used is atomic percentage (Atomic%) 76

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