本研究乃利用二階段單體添加的製備方式，以無乳化劑乳化聚合法於沸騰狀態下，製備具有交聯結構的耐溶劑核心與軟殼層之核殼結構次微米球。將不同比例的MMA與DVB反應一段時間後，添加二階段單體BA製備出核殼結構次微米球，並於室溫下或壓縮程序進行自組裝，建構三維結構之光子晶體。在實驗探討方面，主要針對第一階段轉化率、核心耐溶劑性、二階段單體添加量對成膜性的影響、核心與殼層折射率差對光子晶體膜光學性質的影響以及不同表面官能基改質的影響做討論。 結果顯示，當核心交聯程度達20%即具有耐溶劑性，並於轉化率為85%時製備P(MMA-co-DVB)/PBA核殼結構次微米球，隨著二階段單體BA添加量由3克添加至10克時，其粒徑由263 nm上升至341 nm，殼層玻璃轉移溫度由-21℃下降至-40℃，核心則因為交聯20%使得Tg變化不明顯。由外觀判斷，二階段單體BA添加量達10克時，自組裝後的光子晶體膜即具有成膜性，但其光學性質仍然微弱，其原因為核心與殼層折射率差異過於相近所造成。 另一部份則藉由St的添加，改變核心的折射率，並於核心轉化率85%時製備P(St-co-MMA-co-DVB)/PBA核殼結構次微米球，並將室溫自組裝後的光子晶膜經由一壓縮程序，使原本微弱的結構性色彩變得更鮮明。隨著核心與殼層折射率差異增加，光子能隙亦從原先1~2%微弱的反射強度提升至25%左右；最後則利用不同官能基之單體進行表面改質，藉由改變球與球之間作用力或殼層折射率，改善光子晶體之光學性質。;In this study, robust opal film has been developed by core-shell submicrospheres. Monodispersed P(MMA-co-DVB) / P(BA) core-shell structure submicrospheres were prepared by two-step soap-free emulsion polymerization at boiling state. MMA and DVB were polymerized during a period of time, and then BA was introduced into the above reaction solution and polymerized. Then the latex was dropped onto substrate and self-assembly in room temperature to fabricate the photonic crystal film. The effect of the conversion of core, the solvent resistance properties of core, the amount of shell monomer, the difference of refractive index between core and shell and kinds of shell monomers on the optical and mechanical properties were discussed. The results indicated that the monodispersed, solvent-resistant cores were prepared as the DVB content was higher than 20 wt %. The P(MMA-co-DVB) / P(BA) core/shell submicrospheres were easily prepared when the first step conversion was 85%. The diameters of P(MMA-co-DVB) / P(BA) core/shell submicrospheres were changed from 263 nm to 341 nm and the Tg of shell were decreased from -21 oC to -40 oC by adjusting the amount of shell monomer (BA) from 3g to 10g. The photonic crystal had the film-forming property when amount of shell monomer (BA) reached to 10g, but the optical property was still weak. The optical property can be improved by compressing the photonic crystal film that was self-assembly in room temperature and increasing the difference of refractive index between core and shell by adding styrene at first step. In addition, for the UV-vis result, the reflective intensity were improved from 1~2% to 25%, the photonic crystal film became colorful. On the other hand, the optical properties of photonic crystal film can be improved by adding different monomers into shell to change the interaction between particle to particle and the difference of refractive index between core and shell.