臺灣博碩士論文加值系統

本論文係研究利用未摻雜五環素(Pentacene)及鈉(Na)摻雜的五環素來成長P/N-type有機薄膜，並首次應用這些P/N-type有機薄膜於玻璃上製作有機垂直型雙載子接面電晶體(BJT)。吾人利用SEM來觀察有機薄膜的表面形態、AFM來測量薄膜表面的粗糙程度、EDS來檢視無機物摻雜的有效性。並利用玻璃基板成長有機薄膜製造P/N 二極體來確定摻雜後有機薄膜的正負型，及比較各種不同成長參數所完成二極體的電流-電壓特性。最後再以所得最佳成長參數在玻璃上研製有機垂直型雙載子接面光電晶體。實驗結果證實未摻雜的五環素薄膜具有P-type的特性，而摻雜鈉的五環素薄膜則含有N-type的特性。
本研究使用不同重量比的醯銨鈉無機鹽化合物與五環素混和物共同蒸鍍來得到不同含量的鈉摻。實驗結果顯示，NPN/PNP元件，常溫下摻雜醯銨鈉的元件在照與沒照鎢絲燈光(3mW/cm2)後電流增益/光暗電流比約為1.72/8.17及 1.11/4.09。

In this thesis, we utilized Pentacene and Pentacene doped by Na to prepare P type, and N type organic thin films, respectively. To dope Na, the Pentacene mixed by NaNH2 with various weight ratios were co-evaporated. And then these N/P organic thin films were used to develop organic vertical bipolar junction transistors on glass substrates. We used SEM to observe the films’ morphology; AFM to measure surface roughness and EDS to examine the dopant in the films. In addition, the parameters including the weight ratio of Pentacene to dopant Na in the evaporation, and growth rate were investigated and optimized to prepare organic vertical bipolar junction transistors.
The electric gain/optical gain of the developed vertical type NPN and PNP transistors on glass substrate without and with the illumination of tungsten lamp with light power of 3mW/cm2 are 1.72/8.17, and 1.11/4.09, respectively.

中文摘要I
英文摘要III
目錄IV
附表目錄VI
附圖目錄VII
第一章、前言1
第二章、PN二極體、雙載子接面電晶體元件介紹、有機材料摻雜原理及有機元件電極與電荷注入材料之理論5
§2-1 PN二極體元件結構與工作原理5
§2-2 雙載子接面電晶體元件結構與工作原理6
§2-3 有機垂直雙載子接面電晶體元件結構與工作原理9
§2-4 光電晶體元件結構及工作原理9
§2-5 有機材料摻雜碘與鈉原理 10
§2-5-1 有機材料摻雜碘與鈉之特性及理論10
§2-5-2碘與鈉摻雜有機雙載子光電晶體元件之研究動機11
§2-6有機元件電極與電荷注入材料之理論12
§2-6-1 陽極材料12
§2-6-2 陰極材料13
§2-6-3 電洞注入層(HIL)理論14
§2-6-4 電子注入層(EIL)理論15
第三章、成長系統、製備流程與量測儀器介紹17
§3-1成長系統17
§3-1-1 真空蒸著系統(Thermal Vacuum Evaporation System)17
§3-2有機PN二極體元件製備流程18
§3-2-1 矽基板清洗18
§3-2-2 玻璃基板清洗18
§3-2-3 成長有機薄膜19
§3-3 有機雙極性光電晶體元件製備流程20
§3-3-1 矽基板清洗20
§3-3-2 成長有機薄膜20
§3-4量測儀器20
§3-4-1 原子力顯微鏡（Atomic Force Microscope, AFM）20
§3-4-2 場發射掃瞄式電子顯微鏡（Field Emission Scanning Electron Microscope, FESEM）21
§3-4-3 傅立葉轉換紅外線光譜儀(Fourier transform infrared spectroscopy, FTIR)21
§3-4-4 膜厚量測儀(α-step)22
§3-4-5 光致螢光光譜儀(PL)22
第四章、實驗結果與探討23
§4-1 薄膜特性分析23
§4-1-1 薄膜EDX分析 24
§4-1-2 薄膜SEM分析 24
§4-1-3薄膜成長於矽基板及玻璃基板厚度關係探討25
§4-1-4有機薄膜粗糙度分析25
§4-1-5 AFM 薄膜粗糙度結論27
§4-2 有機薄膜電性分析27
§4-2-1 五環素6毫克摻雜I-V特性27
§4-2-2 五環素9毫克摻雜I-V特性28
§4-2-3 五環素12毫克摻雜I-V特性28
§4-2-4 五環素摻雜NaNH2 I-V特性結論28
§4-3 薄膜總結28
§4-4 垂直型有機雙極性接面電晶體元件之I-V特性分析29
§4-4-1 NPN元件I-V特性分析29
§4-4-2 NPN元件照光I-V特性31
§4-4-3 PNP元件I-V特性分析31
§4-4-4 PNP元件照光I-V特性32
第五章、結論與未來展望33
§5-1結論33
§5-2 未來展望34
參考文獻36
附表40
附圖42

附表目錄
表1 五環素量摻雜醯氨鈉倍數之參數40
表2 五環素摻雜醯氨鈉之EDS成份分析比較表41

附圖目錄
圖1-1電子在有機半導體中的傳遞42
圖2-1 傳統二極體元件結構剖面圖43
圖2-2 傳統二極性元件之電流-電壓特性圖43
圖2-3雙極性電晶體
(a)雙極性電晶體透視圖44
(b)雙極性電晶體剖面圖44
圖2-4 有機垂直雙極性電晶體示意圖
(a)NPN有機垂直雙極性電晶體45
(b)PNP有機垂直雙極性電晶體45
圖2-5 傳統雙極性光電晶體結構剖面圖46
圖2-6 傳統雙極性光電晶體區塊圖46
圖2-7 五環素分子結構圖47
圖2-8 五環素摻雜醋酸鈉、醯氨鈉AFM比較圖
(a) 五環素摻雜20倍醋酸鈉之AFM圖47
(b) 五環素摻雜12倍醯氨鈉之AFM圖48
圖2-9合金功函數與注入能障(Schottky barrier)關係圖49
圖2-10 CuPc結構圖49
圖2-11 HAT結構圖50
圖2-12 P型摻雜層與電極間的能階示意圖50
圖3-1 真空蒸著系統51
圖4-1 未摻雜五環素之SEM分析
(a) 未摻雜五環素在玻璃基板上52
(b) 未摻雜五環素在矽基板上52
圖4-2 五環素摻雜6倍醯氨鈉
(a) 五環素摻雜6倍醯氨鈉在玻璃基板上52
(b) 五環素摻雜6倍醯氨鈉在矽基板上52
圖4-3五環素摻雜12倍醯氨鈉
(a) 五環素摻雜12倍醯氨鈉在玻璃基板上53
(b) 五環素摻雜12倍醯氨鈉在矽基板上53
圖4-4五環素摻雜醯氨鈉倍數與薄膜厚度之關係53
圖4-5未摻雜五環素薄膜AFM粗糙度分析
(a) 未摻雜五環素薄膜成長於玻璃基板上54
(b) 未摻雜五環素薄膜成長於矽基板上54
圖4-6五環素6毫克摻雜NaNH2薄膜AFM粗糙度分析
(a) 摻雜6倍NaNH254
(b) 摻雜9倍NaNH254
(c) 摻雜12倍NaNH254
圖4-7五環素9毫克摻雜NaNH2薄膜AFM粗糙度分析
(a) 摻雜6倍NaNH255
(b) 摻雜9倍NaNH255
(c) 摻雜12倍NaNH255
圖4-8五環素12毫克摻雜NaNH2薄膜AFM粗糙度分析
(a) 摻雜6倍NaNH256
(b) 摻雜9倍NaNH256
(c) 摻雜12倍NaNH256
圖4-9 玻璃基板上成長有機二極體57
圖4-10五環素6毫克摻雜NaNH2的二極體I-V曲線
(a) 摻雜6倍NaNH257
(b) 摻雜9倍NaNH258
(c) 摻雜12倍NaNH258
圖4-11五環素9毫克摻雜NaNH2的二極體I-V曲線
(a) 摻雜6倍NaNH259
(b) 摻雜9倍NaNH259
(c) 摻雜12倍NaNH260
圖4-12五環素12毫克摻雜NaNH2的二極體I-V曲線
(a) 摻雜6倍NaNH261
(b) 摻雜9倍NaNH261
(c) 摻雜12倍NaNH262
圖4-13 NPN架構圖，射極摻雜6倍NaNH263
圖4-14射極摻雜6倍NaNH2 NPN無照光I-V特性
(a) 無照光共射極I-V特性63
(a) 無照光共基極I-V特性64
圖4-15 NPN架構圖，射極摻雜9倍NaNH265
圖4-16射極摻雜9倍NaNH2 NPN無照光I-V特性
(a) 無照光共射極I-V特性65
(a) 無照光共基極I-V特性66
圖4-17 NPN架構圖，射極摻雜12倍NaNH267
圖4-18射極摻雜12倍NaNH2 NPN無照光I-V特性
(a) 無照光共射極I-V特性67
(a) 無照光共基極I-V特性68
圖4-19 NPN電晶體光感應
(a) 射極摻雜6倍NaNH2 NPN照光I-V特性(VBE=0)68
(a) 射極摻雜6倍NaNH2 NPN照光共射極I-V特性69
圖4-20 PNP架構圖，基極摻雜6倍的NaNH270
圖4-21基極摻雜6倍NaNH2 PNP無照光I-V特性
(a) 基極摻雜6倍NaNH2 PNP無照光共射極I-V特性70
(b) 基極摻雜6倍NaNH2 PNP無照光共基極I-V特性71
圖4-22 PNP架構圖，基極摻雜9倍72
圖4-23 基極摻雜9倍NaNH2 PNP無照光I-V特性
(a) 基極摻雜9倍NaNH2 PNP無照光共射極I-V特性72
(b) 基極摻雜9倍NaNH2 PNP無照光共基極I-V特性73
圖4-24 PNP電晶體光感應
(a) 基極摻雜9倍NaNH2 PNP照光共射極I-V特性(VBE=0)74
(b) 基極摻雜9倍NaNH2 PNP照光共射極I-V特性74

[1] K. Yamashita, T. Mori, T. Mizutani, H. Miyazaki, and T. Takeda, “EL properties of organic light-emitting diodes using TPD derivates with diphenylstylyl groups as hole transport layer”, Thin Solid Films, Vol.363, pp.33-36 (2000).
[2] C. O. Poon, F. L. Wong, S. W. Tong, R. Q. Zhang, C. S. Lee, and S. T. Lee, ”Improved performance and stability of organic light-emitting devices with silicon oxy-nitride buffer layer”, Appl. Phys. Lett., Vol.83, pp.1038-1040 (2003).
[3] Z. Bao, A. Dodabalapur, and A. J. Lovinger, ”Soluble and processable regioregular poly (3-hexylthiophene) for thin film field-effect transistor applications with high mobility”, Appl. Phys. Lett., Vol.69, pp.4108-4110 (1996).
[4] Y Jin, Z. Rang, M. I. Nathan, P. P. Ruden, C. R. Newman, and C. D. Frisbie, “Pentacene organic field-effect transistor on metal substrate with spin-coated smoothing layer”, Appl. Phys. Lett., Vol.85, pp.4406-4408 (2004).
[5] S. S. Kim, Y. S. Choi, K. Kim, J. H. Kim, and S. Im, “Fabrication of p-pentacene/n-Si organic photodiodes and Characterization of their photoelectric properties”, Appl. Phys. Lett., Vol.82, pp.639-641, (2002).
[6] J. Lee, S. S. Kim, K. Kim, J. H. Kim, and S. Im, “Correlation between photoelectric and optical absorption spectra of thermally evaporated pentacene films”, Appl. Phys. Lett., Vol.84, pp.1701-1703, (2004).
[7] C. W. Tang, “Two-layer organic photovoltaic cell”, Appl. Phys. Lett., Vol.48, pp.183-185,(1985).
[8] J. Drechsel, B. Mannig, F. Kozlowski, D. Gebeyehu, A. Werner, M. Koch, K. Leo, M. Pfeiffer, “High efficiency organic solar cells based on single or multiple PIN structures”, Thin Solid Films, Vol.451-452, pp.515-517, (2004).
[9] 陳金鑫，黃孝文，”有機電激發光材料與元件”，五南圖書出版公司, (2006).
[10] T. H. Chou, S. F. Chen, Y. K. Fang, S. C. Hou, F. S. Lin, and C. Y. Lin, “Significantly Improved Luminance of Organic Light-Emitting Diodes by Doping Iodine and Nitrogen Treatment”, Japanese Journal of Applied Physics, Vol.46, pp.2753-2757 (2007).
[11] F. Huang, A. G. MacDiarmid, and B. R. Hsieh, “An Iodine-doped polymer light-emitting diode”, Appl. Phys. Lett., Vol.71, pp.2415-2417 (1997).
[12] C. K. Chiang, S. C. Gau, C. R. Fincher, Jr., Y. W. Park, A. G. MacDiarmid, and A. J. Heeger,”Polyacetylene, (Ch)x: N-type and p-type doping and compensation.”, Appl. Phys. Lett., Vol.33, pp.18-20 (1978).
[13] Y. -Y. Lin, D. J. Gundlach, S. F. Nelson, T. N. Jackson, “Pentacene Organic Thin-Film Transistors – molecular Ordering and Mobility.”, IEEE Electron. Device Lett., Vol.18, NO.3, pp.87-89 (1997).
[14] S. P. Park, S. S. Kim, J. H. Kim, C. N. Whang, and S. Im, “Optical and luminescence characteristics of thermally evaporated pentacene films on Si”, Appl. Phys. Lett., Vol.80, pp.2872-2874, (2002).
[15] J. M. Shannon, “A majority-carrier camel diode”, Appl. Phys. Lett., Vol.35, pp.63-65, (1979).
[16] C.Y. Chang, B.S. Wu, Y.K. Fang, R.H. Lee “Optical and electrical current gain in an amorphous silicon bulk barrier phototransistor”, IEEE EDL, Vol.6, pp.3 (1985).
[17] J. Kido, T. Matsumoto, “Bright organic electroluminescent devices having a metal-doped electron-injecting layer.”, Appl. Phys. Lett., Vol.73, pp.2866-2868,(1998).
[18] J. H. Cho, H. S. Lee, Minkyu Hwang, H. H. Choi, W. K. Kim, J. L. Lee, and Kilwon Cho,” Enhancement of Hole Injection in Organic TFTs by Ozone Treatment of Indium Tin Oxide Electrodes”, ECS, Vol.10, pp.H156-H159 (2007).
[19] F.C. Chen, L.J. Kung, T.H. Chen, and Y.S. Lin,” Copper phthalocyanine buffer layer to enhance the charge injection in organic thin-film transistors”, Appl. Phys. Lett., Vol.90, pp.H073504 (2007).
[20] T. Wakimoto, Y, Fukuda, K. Nagayama, A. Yokoi, H. Nakada, M. Tsuchida, “Organic EL Cells Using Alkaline Metal Compounds as Electron Injection Materials.”, IEEE Trans. Electron. Devices, Vol. 44, NO. 8, pp.1245-1248, (1997).
[21] C. Ganzorig, M. Fujihira, “Evidence for alkali metal formation at a cathode interface of organic electroluminescent devices by thermal decomposition of alkali metal carboxylates during their vapor deposition.”, Appl. Phys. Lett., Vol.85, pp.4774-4776,(2001).