Synopsis;
Openly defying Seireitei to obtain an artifact of Kisuke Urahara's prior research- the Houkyuko- Aizen Sosuke forsook Soul Society to carry on his ambitions from Hueco Mundo without interference; declaring his ambition of ascension.
With the Houkyuko - a device to give Hollow Shinigami capabilities, in turn increasing their potential like Hollowfication did for the Vaizard - Aizen set out to create an army of Arrancar. And who better to use against the Shinigami than their principle enemies; the Hollow?
Note; some Arrancar have been known to evolve on their own, without necessitating the Houkyuko.
the Arrancar;
Arrancar are Hollow that have had their masks removed and have gained the powers of a Shinigami. They gain much more humanoid appearance in the process, as well as strength and intelligence beyond the level of a simple Hollow; accompanied by a strong sense of individuality. Like Shinigami, Arrancar possess zanpakutou.
Unlike Shinigami, whose zanpakutou are manifestations of their owner's soul, Arrancar's zanpakutou are manifestations of their former hollow selves. With occasional exceptions, an Arrancar's zanpakutou resembles a regular sword in its unsealed state. When released through a process called Resurrección, part of their original Hollow form is restored, changing their appearance, giving them greater strength, and granting them access to their original abilities.
Segunda;
Segunda is a second transformation which exceeds an Arrancar's Resurreción, drastically increasing their power and abilities in unique ways. Ulquiorra Schiffer claimed he was the only Espada who had attained Segunda to his knowledge.
Note; Segunda is reserved for a very few Espada who have proven their capabilities and earned recommendation from the Captain Commander.