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Vertical stratified microstructures with highly crystalline P3HT network on the surface were formed when depositing from marginal solvents, while lateral phase\u2010separated structures or low P3HT crystallinity were observed for good solvents. The morphological differences came from the solvent effect. In marginal solvents, <jats:italic>p<\/jats:italic>\u2010xylene and dichloromethane, P3HT large\u2010scale microcrystallites were generated in solution, which ensured the priority of P3HT crystalline sequence, and phase separation began in the liquid states. When the PEG matrix began to crystallize, great energy from which the second phase separation was induced drove P3HT crystallites to the surface, resulting in the formation of vertical stratified microstructures with highly crystalline P3HT network on the surface. The method, crystallization\u2010induced phase segregation of crystalline\u2013crystalline blends in marginal solvent, provides a facile way to construct vertically stratified structures, in which P3HT highly crystalline network is favored.<\/jats:p><jats:p><jats:boxed-text content-type=\"graphic\" position=\"anchor\"><jats:graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" mimetype=\"image\/jpeg\" position=\"anchor\" specific-use=\"enlarged-web-image\" xlink:href=\"graphic\/mgra001.jpg\"><jats:alt-text>magnified image<\/jats:alt-text><\/jats:graphic><\/jats:boxed-text>\n<\/jats:p>","DOI":"10.1002\/marc.200900770","type":"journal-article","created":{"date-parts":[[2010,1,5]],"date-time":"2010-01-05T09:58:58Z","timestamp":1262685538000},"page":"532-538","source":"Crossref","is-referenced-by-count":40,"title":["Crystallization\u2010Induced Phase Segregation Based on Double\u2010Crystalline Blends of Poly(3\u2010hexylthiophene) and Poly(ethylene glycol)s"],"prefix":"10.1002","volume":"31","author":[{"given":"Kui","family":"Zhao","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Zicheng","family":"Ding","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Longjian","family":"Xue","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yanchun","family":"Han","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2010,3,24]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/1616-3028(200102)11:1<15::AID-ADFM15>3.0.CO;2-A"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1557\/JMR.2004.0252"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/cm049654n"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/adma.200702505"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/adma.200600623"},{"key":"e_1_2_6_7_2","unstructured":"\u00a0"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1002\/adfm.200601248"},{"key":"e_1_2_6_9_2","unstructured":"\u00a0"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma0482314"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20020118)41:2<329::AID-ANIE329>3.0.CO;2-M"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1038\/nmat1476"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma9619288"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1038\/nmat1779"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.2734387"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1002\/polb.1987.090250508"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1002\/adma.200701519"},{"key":"e_1_2_6_18_2","unstructured":"\u00a0"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevLett.55.1102"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevA.39.783"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1039\/b418109c"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20020118)41:2<329::AID-ANIE329>3.0.CO;2-M"},{"key":"e_1_2_6_23_2","unstructured":"\u00a0"},{"key":"e_1_2_6_24_2","first-page":"2528;","volume":"103","author":"Malik S.","year":"2007","journal-title":"J. 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