本論文主要研究新穎氮碳化矽(SiCN)紫外光感測器及低成本低溫多晶矽(low temperature polysilicon, LTPS)氫氣感測器。氮碳化矽三元化合物是一種較新穎高能隙材料(3.2 ~ 4.4 eV)，其對應光波長為紫外光(ultraviolet, UV)，因此利用氮碳化矽薄膜來作為紫外光感測器(detector)。一般紫外光感測常用高能隙材料有GaN，β-SiC on Si，4H-SiC，diamond以及6H-SiC等。與這些常用材料相比，氮碳化矽較便宜且較易直接成長於矽晶上因此較適合低成本高性能紫外光感測器。本論文係利用快速昇溫化學氣相沉積(RTCVD)系統，以C3H8氣體作為碳(C)原子的來源，成長氮碳化矽薄膜並利用FESEM，XRD，TEM，AFM， PL，PR，HP4145B(I/V)，254 nm UV light source等儀器來分析氮碳化矽薄膜結晶性與光電特性。在矽單晶基板上分別為研製四種不同結構氮碳化矽高溫紫外光偵測器元件即是(1) n-SiCN/p-PS/p-Si (2) n-SiCN/p-SiCN (3) n-SiCN/i-SiCN/p-SiCN and (4) n-SiCN/i-SiCN/p-Si 。
另一方面，吾人利用電化學陽極蝕刻法(electrochemical anodization method)於p(100)單晶矽基板表面蝕刻出多孔矽(porous silicon, PS)層，此多孔矽層具有高電阻特性，可用來抑制紫外光(ultraviolet)偵測元件在高溫環境時所增加的暗電流，且此多孔矽層亦能增加光偵測元件對紫外線的吸光面積，提升光電效率。另外，多孔矽層海綿(sponge-like)的結構有助於在其表面上之磊晶(epitaxy)薄膜的成核與成長。除此之外，多孔矽層高電阻特性亦可作為半絕緣基板(semi-insulating substrate)。因此吾人也利用多孔矽層來研製高性能n-SiCN/p-PS/p-Si異質接面高溫紫外光感測器元件。
此外，由於能源危機及環境污染，許多替代性的能源蓬勃發展。其中氫氣因為是乾淨能源故被列為當今最具吸引力以及取代石油的最終替代能源的優先選項。另一方面，隨著科技的發達，氫氣在化學製程，化工製程，半導體工業與醫療業上亦為十分重要之原料與產物。然而氫氣是一種具有可燃性及爆炸性的氣體，當氫氣體積濃度介於4.65% ~ 93.9%間即會產生爆炸。所以，基於環保及工安兩方面的考量，發展可以迅速偵測並嚴密監控外洩氫氣濃度之氫氣感測器是有其重要性。本論文報導利用準分子雷射退火(excimer laser annealing, ELA)技術在玻璃基板成長的低溫多晶矽薄膜上研製低成本高性能金屬/半導體(MS)蕭特基二極體式氫氣感測器。利用鈀閘極吸附氫氣後，臨限電壓與兩端電容值的改變，作為檢測氫氣的依據。其運用原理是採用鈀金屬對氫氣具有良好的觸媒(catalytic)活性，在含有氫氣的環境中，能將吸附於表面的氫分子(molecule)解離(dissociation)為氫原子(atom)，而部分的氫原子將會擴散穿過鈀金屬並吸附(adsorption)於金屬與氧化層界面，這些氫原子經極化後，會改變界面的電場，造成氧化層與矽半導體界面的蕭特基能障高度改變(Schottky barrier height variation)，因此改變了元件的電性。然而，矽的費米能階容易產生表面態位釘住效應(Fermi level pinning)，使蕭特基能障高度較不受極化氫原子的影響，所以對氫氣之靈敏度也較差。因此吾人並用二氧化鈦(TiO2)材料來增加能障高度變化(barrier height variation)以改善MOS Schottky diode對氫氣吸附能力，進而提升偵測的靈敏度。

In this dissertation, we report the investigations of novel SiCN ultraviolet light detectors and LTPS (low temperature polysilicon) low cost hydrogen sensors. Four type structures including n-SiCN/p-PS/p-Si heterojunction, n-SiCN/p-SiCN homojunction, and n-SiCN/i-SiCN/p-SiCN and n-SiCN/i-SiCN/p-Si junctions, have been developed.
Firstly, we study the n-SiCN/p-silicon heterojunction with porous silicon (PS) buffer layer for low cost and high temperature ultraviolet (UV) detecting applications. The PS layer and the cubic crystalline n-SiCN film were formed on the top of p-(100) silicon substrate by the electrochemical anodization and rapid thermal chemical vapor deposition (RTCVD) sequentially. The PS layer has a high resistivity to suppress the dark current, and provides sponge-like structure to limit strain and cracks development after the post growth cooling, thus favoring nucleation to result a better single crystal SiCN film. Consequently, the developed optical sensing device has a high room temperature (25 °C) photo/dark current ratio (PDCR) 85.4 with and without irradiation of and 254 nm UV light with 0.5 mW/cm2 optical power. Even though at 200 °C the ratio is still equal to 7.42. These results are better than the reported ZnO on GaAs substrate or β-SiC on Si substrate UV detectors without porous treatment.
Next, a novel n-SiCN/p-SiCN homojunction was developed on Si substrate with RTCVD for low cost and high performance ultraviolet detecting applications. The current ratio of the junction under -5 V bias, with and without irradiation of 254 nm UV light are 1940, and 96.3 at room temperature, and 175 °C, respectively. Compared to the reported UV detectors with material of 4H-SiC or β-SiC, the developed n-SiCN/p-SiCN homojunction has better current ratio in both room and elevated temperature.
To raise the detector’s PDCR, both n-SiCN/i-SiCN/p-SiCN and n-SiCN/i-SiCN/p-Si junctions were developed. The measured PDCR of n-SiCN/i-SiCN/p-SiCN and the n-SiCN/i-SiCN/p-Si junctions with and without irradiation of 254 nm UV light under -5 V bias and 0.5 mW/cm2 are 150.26 and 5.42, respectively. Compared to the reported UV detectors with 4H-SiC or β-SiC (3C-SiC), the developed n-SiCN/i-SiCN/p-SiCN homojunction has the better current ratio in both room and high temperatures. Additionally, the Pd/n-LTPS (MS) and Pd/TiO2/n-LTPS (MOS) Schottky diodes fabricated on a glass substrate for hydrogen sensing are reported.
On the other hand, we also investigate the hydrogen detecting performance of Pd/n-LTPS/glass thin film Schottky diodes. The n-LTPS (n-type low temperature polysilicon) is an excimer laser annealed (ELA) and PH3 gas plasma treated amorphous silicon (a-Si) thin film. In addition, we used a TiO2 interface layer to improve hydrogen sensing ability significantly. At room temperature and -2 V bias, the developed MOS Schottky diode exhibited a high signal ratio of 1539.6% to 50 ppm of hydrogen gas, with a fast response time of 40 sec, respectively. The signal ratio is better or comparable with that of other reported MOS type hydrogen gas sensors prepared on Si or III-V compound substrate. Furthermore, the signal ratio is 7.6, 14, and 30 times over other interfering gases of C2H5OH, C2H4, and NH3 at room temperature and a concentration of 8000 ppm at -2 V bias, respectively. Thus, the developed MOS Schottky diode shows promise for the future development and commercialization of a low cost hydrogen sensor.

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