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    • 2. 发明授权
    • Recrystallization method to selenization of thin-film Cu(In,Ga)Se.sub.2
for semiconductor device applications
    • 用于半导体器件应用的薄膜Cu(In,Ga)Se2的硒化的重结晶方法
    • US5436204A
    • 1995-07-25
    • US293826
    • 1994-08-22
    • David S. AlbinJeffrey J. CarapellaJohn R. TuttleMiguel A. ContrerasAndrew M. GaborRommel NoufiAndrew L. Tennant
    • David S. AlbinJeffrey J. CarapellaJohn R. TuttleMiguel A. ContrerasAndrew M. GaborRommel NoufiAndrew L. Tennant
    • C01B19/00C01G3/00C23C14/34C23C30/00H01L21/20H01L21/203H01L21/205H01L21/263H01L21/363H01L31/0296H01L31/032H01L31/04H01L21/302
    • H01L31/0322Y02E10/541Y02P70/521
    • A process for fabricating slightly Cu-poor thin-films of Cu(In,Ga)Se.sub.2 on a substrate for semiconductor device applications includes the steps of forming initially a slightly Cu-rich, phase separated, mixture of Cu(In,Ga)Se.sub.2 :Cu.sub.x Se on the substrate in solid form followed by exposure of the Cu(In,Ga)Se.sub.2 :Cu.sub.x Se solid mixture to an overpressure of Se vapor and (In,Ga) vapor for deposition on the Cu(In,Ga)Se.sub.2 :Cu.sub.x Se solid mixture while simultaneously increasing the temperature of the solid mixture toward a recrystallization temperature (about 550.degree. C.) at which Cu(In,Ga)Se.sub.2 is solid and Cu.sub.x Se is liquid. The (In,Ga) flux is terminated while the Se overpressure flux and the recrystallization temperature are maintained to recrystallize the Cu.sub.x Se with the (In, Ga) that was deposited during the temperature transition and with the Se vapor to form the thin-film of slightly Cu-poor Cu.sub.x (In,Ga).sub.y Se.sub.z. The initial Cu-rich, phase separated large grain mixture of Cu(In,Ga)Se.sub.2 :Cu.sub.x Se can be made by sequentially depositing or co-depositing the metal precursors, Cu and (In, Ga), on the substrate at room temperature, ramping up the thin-film temperature in the presence of Se overpressure to a moderate anneal temperature (about 450.degree. C.) and holding that temperature and the Se overpressure for an annealing period. A nonselenizing, low temperature anneal at about 100.degree. C. can also be used to homogenize the precursors on the substrates before the selenizing, moderate temperature anneal.
    • 在用于半导体器件的衬底上制造Cu(In,Ga)Se2的略微不合铜的薄膜的工艺包括以下步骤:首先形成Cu(In,Ga)Se 2的稍微富Cu,相分离的混合物 :在固体形式的衬底上,然后将Cu(In,Ga)Se 2:CuxSe固体混合物暴露于Se蒸气和(In,Ga)蒸气的过压,沉积在Cu(In,Ga)Se 2:CuxSe上 固体混合物同时将固体混合物的温度升高至重结晶温度(约550℃),其中Cu(In,Ga)Se 2为固体,CuxSe为液体。 (In,Ga)通量终止,同时保持Se超压通量和再结晶温度,以在温度转变期间沉积的(In,Ga)和Se蒸气重结晶CuxSe,形成薄膜 轻微Cu-Cux(In,Ga)ySez。 Cu(In,Ga)Se2:CuxSe的初始富Cu相分离的大晶粒混合物可以通过在室温下依次沉积或共沉积金属前体Cu和(In,Ga) 在存在Se超压的情况下将薄膜温度升高到适度退火温度(约450℃),并保持该温度和Se超压退火时间。 在硒化,中等温度退火之前,也可以在约100℃下进行非硒化低温退火,以使基板上的前体均匀化。