Recycling of Rejects.

Process for cleaning silicon with popcorn-like surfaces and structures
Process for cleaning silicon with popcorn-like surfaces and structures

Manufacturers can get more out of porous silicon

DECKER-Anla­gen­bau — a spe­cia­list in wet-che­mi­cal pro­ces­ses — has laun­ched a sili­con puri­fi­ca­ti­on sys­tem onto the mar­ket that can be used to tre­at porous sili­con that is dif­fi­cult to clean. The clea­ned sili­con is then sui­ta­ble for the pro­duc­tion of high-per­for­mance solar cells and can be mar­ke­ted with cor­re­spon­din­gly hig­her yields.

Despi­te good long-term fore­casts, the solar indus­try curr­ent­ly has to bridge a peri­od of low pri­ces. Cal­cu­la­ti­ons are cor­re­spon­din­gly tough. Com­pa­nies are the­r­e­fo­re inves­t­ing hea­vi­ly in the deve­lo­p­ment of effi­ci­ent pro­ces­ses for all stages of the pro­cess chain. For sili­con manu­fac­tu­r­ers, upgrading impu­re sili­con to high-qua­li­ty solar sili­con offers an oppor­tu­ni­ty to increase yields.

Sili­con with a lower degree of puri­ty is crea­ted in the edge are­as of the crys­tal during the pro­duc­tion of high-puri­ty sili­con. During crys­tal growth, den­dri­te for­ma­ti­on occurs at the edge are­as, an unde­si­ra­ble dis­rup­ti­on of the crys­tal struc­tu­re and pos­si­bly the depo­si­ti­on of metals, car­bons or other sub­s­tances on this fis­su­red sur­face. The­se are unde­si­ra­ble struc­tures that can occur both in the Flui­di­zed Bed Reac­tor FBR and in the Sie­mens pro­cess. The addi­ti­on of metals is known to lead to a lower mino­ri­ty car­ri­er life­time, which redu­ces the effi­ci­en­cy of the solar sili­con. Other cau­ses of sili­con con­ta­mi­na­ti­on on the sur­face and just below are the rapid dif­fu­si­on of metal atoms such as nickel or cop­per into the sili­con at room tem­pe­ra­tu­re and con­ta­mi­na­ti­on during trans­por­ta­ti­on, crus­hing, sto­rage and pack­a­ging.

Mate­ri­al con­ta­mi­na­ted in this way achie­ves lower pri­ces due to its lower qua­li­ty. High-puri­ty sili­con has a puri­ty level of 10 ppb(w) in rela­ti­on to the metal con­tent and char­ge car­ri­er life­ti­mes of 10,000 nano­se­conds. The requi­re­ments for PV sili­con are lower, but are con­ti­nuous­ly incre­asing.

Con­ta­mi­na­ted mate­ri­al can be upgraded through appro­pria­te clea­ning. A hig­her degree of puri­ty also has a posi­ti­ve effect on the per­for­mance of CZ pul­lers, for exam­p­le. Howe­ver, clea­ning porous sili­con chunks is a com­plex task due to the com­pli­ca­ted pop­corn-like sur­face of the mate­ri­al. The mate­ri­al has cracks, fis­su­res and fis­su­res and the­r­e­fo­re has a very lar­ge sur­face area that is dif­fi­cult to reach with clea­ning media. Rin­sing and dry­ing mate­ri­als with such fur­ro­wed sur­faces is just as chal­len­ging.

Goal: High throughput at low cost

Wet-che­mi­cal pro­ces­ses with both alka­li­ne and aci­dic clea­ning media or com­bi­ned pro­ces­ses are sui­ta­ble for sili­con clea­ning. The mate­ri­al to be clea­ned is por­tio­ned and moved hori­zon­tal­ly and ver­ti­cal­ly in rota­ting bas­kets or drums.

A ful­ly auto­ma­ted pro­cess is requi­red for the sili­con as it pas­ses through the wet-che­mi­cal clea­ning pro­cess. But how can it be ensu­red that the cre­vices and cracks are also clea­ned and rin­sed as requi­red? How can a dry­ing pro­cess be desi­gned that simul­ta­neous­ly allows a high mate­ri­al through­put at com­pe­ti­ti­ve cos­ts?

Fast cleaning of porous silicon down to the ppbw range

DECKER sol­ves the­se issues by trans­fer­ring the clea­ning pro­cess to a con­vey­or belt. The sili­con chunks are gra­nu­la­ted to allow access to the sur­faces hid­den in cracks and cre­vices. The respec­ti­ve medi­um is sucked by vacu­um through a defi­ned field on the belt on which the sili­con lies. In this way, the pro­cess sol­ves qua­li­ty and effi­ci­en­cy pro­blems inher­ent in the clas­sic pro­cess, as etching pro­ces­ses insi­de bas­kets take lon­ger and are less pre­cise than on their expo­sed sur­faces. The cos­ts for belt fil­ters depend on various para­me­ters — amor­tiza­ti­on times of around one year can be achie­ved under cer­tain con­di­ti­ons.

This is ground­brea­king in various respects. The belt fil­ter vari­ant has a posi­ti­ve effect on many pro­cess para­me­ters: It saves cos­ts and time. Savings in ener­gy and che­mi­cals have a posi­ti­ve impact on the envi­ron­ment. The most important advan­ce, howe­ver, is that the tech­no­lo­gy has ope­ned up the pos­si­bi­li­ty of using it on an indus­tri­al sca­le. Last year, the pro­cess recei­ved the Inno­va­ti­on Award at the Inter­so­lar trade fair. The puri­fied sili­con has a puri­ty level of 6N and bet­ter, depen­ding on the bulk qua­li­ty.

The opti­miza­ti­on of sys­tems to increase pro­duc­tion while redu­cing cos­ts is of gre­at importance for the future of solar com­pa­nies. The sili­con gra­nu­la­te etching sys­tem with belt fil­ter now enables manu­fac­tu­r­ers to upgrade porous, con­ta­mi­na­ted sili­con quick­ly and cost-effec­tively.